Personal care compositions containing complexing polyelectrolytes

ABSTRACT

Compositions of the invention contain, in a cosmetically acceptable aqueous medium, a) a cationic polyelectrolyte, b) at least one surfactant; and (c) from about 0.01 to about 1.2 weight percent of an anionic polyelectrolyte, where the weight ratio of the anionic polyelectrolyte to the cationic polyelectrolyte is from about 0.05 to about 1.2, and where the composition exhibits a viscosity change that is below a minimum significant-change-threshold (Δηmin) and exhibits no measurable yield stress or increase in yield stress value when compared to a substantially identical composition that does not contain from about 0.01 to about 1.2 weight percent of the anionic polyelectrolyte, at a weight ratio of anionic polyelectrolyte to cationic polyelectrolyte of from about 0.05 to about 1.2.

This application claims the benefit of U.S. Provisional Application62/352,713 filed Jun. 21, 2016, the complete disclosure of which ishereby incorporated herein by reference for all purposes.

FIELD

The present invention relates to personal care compositions containingcomplexing polyelectrolyte benefit ingredients.

BACKGROUND

Keratinous surfaces (e.g. skin and hair) are typically cleaned usingsurfactant-based compositions to remove dirt, soils and excess sebum.However, the cleansing process has disadvantages in that it removesessential/advantageous components from the keratinous surfaces duringcleansing. This can lead to an unpleasant feel, e.g., hair can bedraggy, entangled and unmanageable, and have a loss of softness andshine, and/or skin or scalp can feel dry, tight and/or itchy and in somecases show redness. Further, it is desirable to provide benefits fromcleansing compositions beyond foaming and removal of dirt, soils andexcess sebum. A variety of approaches have been developed to alleviatethe disadvantages from the cleansing process and to enhance additionalbenefits beyond foaming and cleansing. For example, cleansingcompositions can comprise (in addition to surfactants) oils likesilicone oils, vegetable oils and mineral oils to provide e.g. a softfeel and enhanced moisturization to the cleaned surfaces. It is alsovery common to incorporate cationic components (in most cases cationicpolymers) into cleansing compositions to provide enhanced sensorialattributes to the cleaned surfaces, e.g. softness, or improvedfunctional qualities, e.g. detangling and anti-static benefits. Thesetypes of additives in cleansing compositions are usually referred to asconditioning agents. Cleansing compositions can also contain additionalbenefit agents such as zinc pyrithione, salicylic acid or hyaluronicacid. In order for these conditioning agents and the benefit agents toperform, they have to be deposited during the cleansing process onto thesurface (e.g. skin and hair).

A common challenge encountered in cleansing compositions is efficacy ofdeposition of conditioning agents and benefit agents onto the cleanedsurfaces. Typically, only a fraction of the agents is deposited and therest is washed/rinsed off. Keratinous surfaces characteristically havesome anionic surface charge; consequently cationic components can adhereto a certain degree onto the keratinous surfaces via electrostaticinteraction.

Therefore, cationic components, cationic polymers in particular, areused in cleansing compositions as conditioning agents. Through a processtypically referred to as “coacervation” or “complexation” or “dilutionprecipitation”, cationic polymers can improve deposition efficacy ofconditioning agents such as emollients, oils, other benefit agents andthe cationic polymers themselves. In this process, the cationic polymerforms insoluble complexes with anionic surfactant during use of thecleansing composition, i.e. upon dilution. These insoluble complexes orcoacervates can enhance deposition efficacy of the cationic polymers aswell as water-insoluble components such as oils.

The concept of combining anionic surfactant and cationic polymer is usedin many cleansing compositions today. Coacervate formation is dependentupon a variety of criteria such as molecular weight, charge density, pH,and temperature. Coacervate systems and the effect of these parametershave previously been studied and disclosed in, for example, J. Caelles,et al., Cosmetics & Toiletries, Vol. 106, April 1991, pp 49-54, C. J.van Oss, J. Dispersion Science and Technology, Vol. 9 (5,6), 1988-89, pp561-573, D. J. Burgess, J. of Colloid and Interface Science, Vol. 140,No. 1, November 1990, pp 227-238, S. Zhou et al., Langmuir, 20, 2004,8482-8489, and C. Lepilleur et al., J. Cosmet. Sci., 62, March/April2011, 161-177. Consequently, approaches to improve the deposition fromcleansing compositions include optimization of the cationic polymer aswell as of the surfactant system. Optimization of the cationic polymerincludes variation of cationic charge density, molecular weight,backbone chemistry and chemistry of the cationic moiety. The surfactantsystem in the cleansing composition is typically adjusted to thespecific cationic polymer utilized to enhance efficiency, compatibilityand formulation stability (or vice versa). Several examples of theseapproaches are disclosed in U.S Pat. Application No. 2003/0108507 andreferences therein.

However, this reference also discloses a deposition efficacy of only2-3% (200-300 ppm/% active level in formulation) for small dispersedactives (that is, benefit agent materials that are insoluble in thecleansing formulation and exist as particles or droplets suspended inthe cleansing formulation) having a size of less than or equal to 2 μm.A deposition efficacy of only 2-3% shows the general need for improvingdeposition efficacy from cleanser formulations. Further, the utilizationof complexation of anionic surfactants and cationic polymer leads to thedeposition of certain amounts of anionic surfactant, present in thecoacervate, onto the keratinous surface. This surfactant deposition isundesirable, as anionic surfactants can exhibit high irritationpotential when left on skin, and anionic surfactants can denature thekeratin components of skin and hair, leading to undesirablemorphological changes in these substrates.

Additionally, compositions utilizing complexation of anionic surfactantand cationic polymer typically do not provide any enhancement/aid ofdepositing water-soluble benefit agents because such benefit agents arenot efficiently captured in the polymer-surfactant coacervates upondilution and thus, are not deposited.

Another approach to enhance deposition efficacy of certain benefitagents described in the prior art is introducing cationic charges to thebenefit agents such as emollients, humectants, and waxes. The cationiccharges can facilitate adhesion of benefit agents onto surfaces withanionic surface charges such as hair and skin. However, such an approachrequires chemical modification of the benefit agent with additionalcationic moieties or encapsulation of the benefit agent with cationicmaterials—both of which may or may not be feasible.

It is reported in the prior art that presence of anionic polymer incompositions with cationic polymer and anionic surfactant does not leadto any improvement of deposition efficacy. For example, anionic rheologymodifier polymers like Carbomer and Acrylates Copolymer have been shownto have detrimental effects on deposition efficacy, as e.g. disclosed inWO 2014/137859 A1. Specifically, this reference states that the presenceof typical rheology polymers such as anionic acrylic copolymers (e.g.Carbopols) does not improve deposition efficacy of silicone oils.Further, they even severely reduce the deposition efficacy of siliconeoils when the silicone oils are of smaller particle size (e.g. averageoil droplet size of less than 5 micrometers). This reference furtherstates that the “silicone deposition is inversely proportional to theamount of the acrylic stabilizer thickener present”. The referencediscloses the use of a nonionic amphiphilic rheology modifying polymerto stabilize the composition “without interfering with the deposition ofthe silicone material” and is silent on how to improve depositionefficacy.

In summary, despite the various approaches used in the prior art toimprove conditioning and deposition efficacy from cleansingformulations, there still remain disadvantages to the prior art, suchas: low deposition efficacy, potential irritation from deposition ofsurfactant, limited compatibility with anionic polymers, and lack of aidin deposition of water-soluble components other than surfactants. Assuch, it remains desirable to provide improved cleansing compositionswith optimum performance and enhanced deposition efficacy.

SUMMARY OF THE INVENTION

The present invention provides compositions comprising, in acosmetically acceptable aqueous medium, a) a cationic polyelectrolyte,b) at least one surfactant; and c) from about 0.01 weight percent toabout 1.2 weight percent of an anionic polyelectrolyte. The weight ratioof anionic polyelectrolyte to cationic polyelectrolyte is from about0.05 to about 1.2.

Compositions of the present invention exhibit a viscosity change that isbelow a minimum significant-change-threshold (Δη_(min)) and exhibit nomeasurable yield stress or increase in yield stress value when comparedto a substantially identical composition that does not contain fromabout 0.01 weight percent to about 1.2 weight percent of the anionicpolyelectrolyte, at a weight ratio of anionic polyelectrolyte tocationic polyelectrolyte of from about 0.05 to about 1.2.

DETAILED DESCRIPTION OF THE INVENTION

Cleansing compositions of the present invention comprise combinations ofcationic and anionic polyelectrolytes. The amount of anionicpolyelectrolyte is selected such that the anionic polyelectrolyte issufficient to increase the amount of Dry Precipitate Mass Yield upondilution and maintain effective cleansing efficacy without the undesiredeffect of changing the rheology properties of the composition. If theweight ratio of anionic polyelectrolyte to cationic polyelectrolyte isfrom about 0.05 to about 1.2, the anionic polyelectrolytes do notincrease the Dry Precipitate Mass Yield.

The specific combination of the anionic polyelectrolyte(s) and thecationic polyelectrolyte(s) in a surfactant system as described hereinis referred to as the “Polyelectrolyte Conditioning System”.“Polyelectrolyte Conditioning System”, as used herein, means acombination of anionic polyelectrolyte(s) and cationicpolyelectrolyte(s), where the anionic and cationic polyelectrolyte(s)are present at a weight ratio of anionic polyelectrolyte to cationicpolyelectrolyte of from about 0.05 to about 1.2, and the concentrationof the anionic polyelectrolyte based on total weight of the cleansingcomposition is from about 0.01 to about 1.2 wt %.

Compositions of the present invention that contain such aPolyelectrolyte Conditioning System exhibit an improved depositionefficacy of conditioning agents and benefit agents, compared to similarcompositions that do not include such a Polyelectrolyte ConditioningSystem, as well as provide additional benefits, e.g. a modified skinfeel after application or a reduced amount of deposited surfactant.Preferred weight ratios of anionic to cationic polyelectrolyte includefrom about 0.05 to about 1.2, or from about 0.1 to about 1.2, or fromabout 0.1 to about 1. The presence of the anionic polyelectrolyte withinthe specific range increases the Dry Precipitate Mass Yield upondilution, measured as described below, by 10% or more compared to asubstantially identical composition that does not contain such an amountof anionic polyelectrolyte. More preferably the Dry Precipitate MassYield upon dilution is increased by 20% or more, or even more preferablyby 40% or more.

As noted above, the weight ratio of anionic polyelectrolyte to cationicpolyelectrolyte is crucial. Typically, at ratios of about 0.05 to about1.2, the compositions exhibit an increased Dry Precipitate Mass Yieldupon dilution. Depending on the type of polyelectrolytes, the surfactantsystem and other formulation parameters, e.g. salt level, the optimalweight ratio of anionic to cationic polyelectrolyte to achieve themaximum Dry Precipitate Mass Yield may vary within this range. Anincrease in the Dry Precipitate Mass Yield upon dilution of a cleansingcomposition is an indication of an improved efficacy in deposition ofconditioning agents and benefit agents. Further, an increase in the DryPrecipitate Mass Yield is an indication that the anionic polyelectrolyteis part of the coacervates formed upon dilution and, thus, is alsodeposited. However, incorporating too much anionic polyelectrolyte intothe composition, compared to the cationic polyelectrolyte, i.e. when theratio of anionic polyelectrolyte mass to cationic polyelectrolyte massis greater than about 1.2, results in no improvement, or even a decreasein performance, compared to the composition with no anionicpolyelectrolyte.

Where applicable, chemicals are specified according to their INCI Name.Additional information, including suppliers and trade names, can befound under the appropriate INCI monograph in the International CosmeticIngredient Dictionary and Handbook, 15^(th) Edition published by thePersonal Care Products Council (PCPC), Washington D.C., also availableonline via the PCPC On-Line Infobase athttp://online.personalcarecouncil.org/jsp/Home.jsp.

All percentages listed in this specification are percentages by weight,unless otherwise specifically mentioned. Percentages and weights ofcomponents like polyelectrolyte, surfactant, salt, polymers, acids etc.listed in this specification are percentages and weights of activematter of a component excluding e.g. solvents like the water of anaqueous sodium chloride solution added to a composition.

As used herein, “substantially identical composition” means acomposition that is substantially the same as compositions of thepresent invention, but for the relative amounts of anionicpolyelectrolyte and cationic polyelectrolyte.

As used herein, “wt %” refers to weight percent, i.e. % weight/weight;e.g. 5 g Sodium Chloride in 95 g water is 5 wt % active Sodium Chloridein aqueous solution.

Anionic Polyelectrolyte

An anionic polyelectrolyte is a polymer bearing a plurality of anioniccharges, i.e. the polyelectrolyte contains monomers or repeat unitsbearing anionic moieties. Suitable moieties bearing anionic charge canbe, but are not limited to CO₂ ⁻, SO₃ ⁻, SO₄ ⁻, PO₃ ²⁻, and PO₄ ²⁻.Compositions of the present invention contain from about 0.01 wt % toabout 1.2 wt % anionic polyelectrolyte.

The anionic polyelectrolyte has a charge density of about 0.1milliequivalents per gram (meq/g) or more, more preferably from about0.1 to 10 meq/g, even more preferably from about 0.5 to 5 meq/g and evenmore preferably from about 0.5 to 4 meq/g and a weight average molecularweight (Mw) of about 10,000 g/mol or more, more preferably from about50,000 g/mol or more. For non-crosslinked anionic polyelectrolytes themolecular weight is from about 50,000 to 3,000,000 g/mol and morepreferably from about 50,000 g/mol to 1,000,000 g/mol. Cross-linkedpolyelectrolytes are typically defined by their primary particle sizerather than a molecular weight. Preferred primary particle sizes forcross-linked anionic polyelectrolytes are about 0.01 micrometer (μm) ormore, more preferred about 0.1 μm or more, and 1000 μm or less, morepreferred about 100 μm or less. Examples for cross-linked anionicpolyelectrolytes are, e.g. Acrylates Copolymer like Carbopol® Aqua SF-1,with a primary particle size of about 0.2 μm, and polyacrylate superabsorbent polymer particles with sizes of about 25-500 μm.

Suitable anionic polyelectrolytes include, but are not limited to, 1)polyelectrolytes derived from ethylenically unsaturated monomerscontaining anionic or anionically ionizable monomers, 2) anionic andanionically ionizable polysaccharides and polysaccharide derivatives and3) other anionic polyelectrolytes such as anionic/anionically ionizablepolypeptides/proteins, anionic/anionically ionizable hybrid (co)polymerscontaining natural polymer chains (like e.g. polysaccharide or proteinchains) as well as synthetic polymer chains (like e.g. polyethyleneglycol or acrylate (co)polymer).

Non limiting examples of such polyelectrolytes are described under theappropriate INCI monographs in the International Cosmetic IngredientDictionary and Handbook, 15^(th) Edition published by the Personal CareProducts Council (PCPC), Washington D.C.

Polyelectrolytes derived from ethylenically unsaturated monomerscontaining anionic/anionically ionizable monomers include, but are notlimited to (a) linear non-crosslinked (co)polymers, includingnon-crosslinked alkali-swellable emulsion (ASE) polymers, (b)crosslinked (co)polymers, including crosslinked ASE polymers (xASE), and(c) hydrophobically modified derivatives of (co)polymers described under(a) and (b), including non-crosslinked and crosslinked hydrophobicallymodified alkali-swellable emulsion (HASE and xHASE) polymers.

Examples of anionic/anionically ionizable ethylenically unsaturatedmonomers include acrylic acid, methacrylic acid, vinyl sulfonic acid,vinyl sulforic acid, vinyl phosphonic acid, vinyl phosphoric acid, vinylboronic acid, citraconic acid, maleic acid, futmaric acid, crotonicacid, itaconic acid, methacryloxyethyl phosphate, methacryloxyethylsulfuric acid, methacryloxyethyl sulfonic acid and2-acrylamidomethylpropane sulfonic acid (AMPSA), 2-methyl-2-propenoicacid ethyl-2-phosphate ester (-HEMA-phosphate), methacryloyloxy PPG-7phosphate, beta-carboxyethyl acrylate, 3-acrylamido-3-methylbutanoicacid (AMBA), and mixtures thereof.

As used herein, the term “(co)polymer” is meant to includepolyelectrolytes derived from essentially one type of monomer(homopolymer) as well as polyelectrolytes derived from more than onetype of monomer (copolymer).

The anionic polyelectrolytes derived from ethylenically unsaturatedmonomers of the invention can be synthesized via free radicalpolymerization techniques known in the art. In another aspect bulkpolymerization, solvent polymerization, precipitation polymerization, oremulsion polymerization techniques can be used to synthesize the anionicpolyelectrolytes of the invention derived from ethylenically unsaturatedmonomers.

As used herein the term “linear non-crosslinked (co)polymer” of theinvention, refers to an anionic polyelectrolyte made from ethylenicallyunsaturated monomers, containing one or more anionic/anionicallyionizable ethylenically unsaturated monomers and optionally one or morenonionic or amphoteric ethylenically unsaturated monomers. Examples fornonionic or amphoteric ethylenically unsaturated monomers include, butare not limited to ethyl (meth)acrylate, butyl (meth)acrylate, vinylformate, vinyl acetate, 1-methylvinyl acetate, vinyl propionate, vinylbutyrate, (meth)acrylamide, dimethyl acrylamide, sulfobetaine acrylates,e.g. 3-methacrylamidopropyldimethylammonio propanesulfonate, andmixtures thereof. Examples of anionic linear non-crosslinked(co)polymers include, but are in no way limited to poly(meth)acrylicacid homopolymers or acrylamide-(meth)acrylic acid copolymers. As usedherein, the term “(meth)acrylic” acid is meant to include thecorresponding methyl derivatives of acrylic acid, and “(meth)acrylate”is meant to include the corresponding methyl derivatives of alkylacrylate and salt forms of acrylic acid. For example, “(meth)acrylic”acid refers to acrylic acid and/or methacrylic acid and “(meth)acrylate”refers to alkyl acrylate and/or alkyl methacrylate and “sodium(meth)acrylate” refers to sodium acrylate and/or sodium methacrylate.The linear non-crosslinked (co)polymer is not hydrophobically modified.

As used herein the term “crosslinked (co)polymer” of the inventionrefers to a crosslinked anionic polyelectrolyte made from ethylenicallyunsaturated monomers. Specifically, it is a crosslinked derivative of alinear non-crosslinked (co)polymer as described above. Crosslinking maybe achieved via a variety of techniques known to those skilled in theart, e.g. copolymerization with multifunctional ethylenicallyunsaturated monomers or post-polymerization reactions to inducecrosslinking. Examples include, but are not limited to, Carbomers andacrylates crosspolymers. Examples for Carbomers are Carbopol® 934, 940,980, Ultrez 10, Ultrez 30, ETD2050, 2984 from Lubrizol, Inc. or Ashland®940, 941, 980, 981 from Ashland, Inc. An example for acrylatescrosspolymer is Acrylates Crosspolymer-4 (Carbopol® Aqua SF-2 fromLubrizol, Inc.). Other examples include superabsorbent polymers, i.e.crosslinked sodium polyacrylate particles.

As used herein the term “hydrophobically modified (co)polymers”, refersto linear non-crosslinked and crosslinked (co)polymer containinghydrophobic monomers. Specifically, “hydrophobically modified” meansthat the polyelectrolyte contains some amount of monomer(s) containing ahydrophobic side group (a hydrophobic monomer, or also referred to asassociative monomer). Typically, the amount of monomer(s) containing ahydrophobic side group is from about 0.1 wt % to about 20 wt %, moretypically about 0.5 wt % to about 10 wt %, and even more typically fromabout 1 wt % to about 5 wt %. They may optionally contain a crosslinkerand/or may optionally be a crosslinked (co)polymer. Examples areAcrylates/C10-30Alkyl Acrylate Crosspolymers (Carbopol® ETD2020, Ultrez20 from Lubrizol, Inc.) and Acrylates/Vinyl Isodecanoate Crosspolymer(Stabylen 30 from 3V Sigma, Inc.).

“Non-hydrophobically modified” as used herein, means that thepolyelectrolyte has no or only minor amounts of monomers containing ahydrophobic side group (a hydrophobic monomer, or also referred to asassociative monomer). Typically, the amount of monomer(s) containing ahydrophobic side group is about 1 wt % or lower, more typically about0.5 wt % or lower, and even more typically about 0.1 wt % or lower.Exceptions are crosslinker monomers/molecules, which may have sidechains with greater than 4 carbon atoms, but are not considered ahydrophobic monomer (and their use level in the polyelectrolyte istypically low, i.e. less than 1 wt %).

As used herein the term “alkali-swellable emulsion polymer” or “ASEpolymer”, refers to a polyelectrolyte made from ethylenicallyunsaturated monomers, e.g. being an acrylate or vinyl (co)polymer, andwherein the polymer contains anionically-ionizable monomers such thatthey become ionized and swell and/or dissolve in aqueous solutions uponaddition of base (alkali). The ASE polymer may optionally contain acrosslinker and/or may optionally be a crosslinked polymer (xASE). Inone embodiment, the ASE or xASE polymer is an acrylates (co)polymerconsisting of one or more monomers of (meth)acrylic acid and/or one oftheir simple alkyl-esters (including methyl-, ethyl-, propyl-,butyl-ester) and simple hydroxyalkyl-esters (includinghydroxyethyl-ester, hydroxybutyl-ester) and simple alkoxyalkyl-esters(including methoxy ethyl-ester, ethoxyethyl-ester). “Simple” alkyl esterrefers to the alkyl-group having from 1 to 4 carbons. The amount ofsimple alkyl ester (meth)acrylate monomer in the polymer ranges from0-80 wt %, 10-70 wt %, 20-70 wt %, 30-70 wt %, 30-60 wt %. Specificexamples of simple alkyl ester (meth)acrylate monomers includemethyl(meth)acrylate, ethyl(meth)acrylate, butyl (meth)acrylate,isobutyl (meth)acrylate, hydroxyethyl(meth)acrylate,hydroxypropyl(meth)acrylate, methoxyethyl(meth)acrylate, ethoxyethyl(meth)acrylate. Examples of ASE polymers are Acrylates Copolymer (e.g.Carbopol, Aqua SF-1 from Lubrizol, Inc. or Eliclear™ 4U from Seppic,Inc.) or Potassium Acrylates Copolymer (EX-968 and EX-1112 fromLubrizol, Inc.).

As used herein the term “hydrophobically modified alkali swellableemulsion polymer” or “HASE polymer”, including “xHASE polymer”, refersto ASE polymers and xASE polymers, respectively, containing hydrophobicmonomers (see above for definition of “hydrophobically modified”).Example of a HASE polymer is Polyacrylate-33 (Rheomer™ 33 from Solvay,Inc.) and for xHASE e.g. Acrylates/Steareth-20 Methacrylate crosspolymer(Aculyn™ 88 from Dow, Inc.).

Hydrophobic monomers (also referred to as “associative” monomers) usedin hydrophobically modified polyelectrolytes are described for examplein U.S. Pat. Nos. 5,292,843, 6,897,253, 7,288,616, 3,035,004, and U.S.Patent Publication No. 2006/0270563, the contents each of which ishereby incorporated by reference in their entirety.

As used herein, the term “non-crosslinked” refers to a (co)polymer thatis substantially free of covalent bond linkages between polymer chains.

As used herein, the term “crosslinked” refers to a (co)polymer with someamounts of covalent bond linkages between polymer chains. Such bondlinkages are generated by addition of some amounts of crosslinkingmonomers to the (co)polymer during the polymerization process. Examplesof crosslinkers are allyl ethers of pentaerythritol, allyl ethers ofsucrose, or allyl ethers of propylene, or trimethylolpropanetriacrylate, ethylene glycol dimethacrylate. Additional crosslinkers aredescribed in U.S. Pat. No. 9,187,590 B2, the contents of which areincorporated herein by reference.

The anionic polyelectrolyte derived from ethylenically unsaturatedmonomers can also contain other monomers. For example, vinyl esters suchas: vinyl acetate, vinyl propionate, N-vinylamides such as:N-vinylpyrrolidione, N-vinylcaprolactam, N-vinylformamide, andN-vinylacetamide, and vinyl ethers such as: methyl vinyl ether, ethylvinyl ether, butyl vinyl ether, and hydroxybutyl vinyl ether, andethylenically unsaturated aryl compounds, such as: styrene, acetoxyethyl(meth)acrylate, and (meth)acrylamides such as: (meth)acrylamide,dimethylacrylamide, N-methylol (meth)acrylamide,N-butoxyethyl(meth)acrylamide, N,N-dimethyl (meth)acrylamide,N-isopropyl(meth)acrylamide, N-tert-butyl (meth)acrylamide, andethylenically unsaturated alkyl esters of dicarboxylic acid monomers,such as: butyl methyl maleate.

Anionic and anionically modified polysaccharides and polysaccharidederivatives include, but are not limited to:

-   -   a. naturally occurring anionic polysaccharides: alginates        (alginic acid), pectin, carrageenan, xanthan, hyaluronic acid,        chondroitin sulfate, gum Arabic, gum karaya, gum traganth,        arabinoxylans, heparan sulfate, and    -   b. anionically modified polysaccharides: include starches, gums,        cellulosics such as carboxy methyl starch, starch phosphate,        hydroxypropyl starch phosphate, starch sulfate,        starch-2-hydroxypropylcitrate, carboxymethyl guar, carboxymethyl        hydroxypropyl guar, other anionic galactomannan derivatives,        carboxy methyl cellulose (INCI name: Cellulose Gum), e.g. as        Aqualon™ Sodium CMC from Ashland, Inc., or as Walocel™ CRT from        Dow, Inc., polyanionic cellulose, cellulose sulfate, cellulose        phosphate, and carboxyethyl cellulose, and other polysaccharides        like e.g. dextran and dextrin, like e.g. dextran/dextrin        sulfate.        Other anionic polyelectrolytes include anionic/anionically        ionizable proteins, anionic polypeptides, e.g., polyglutamic        acid, polyaspartic acid, and other anionic copolymers such as        polynucleic acids.

Cationic Polyelectrolyte

A cationic polyelectrolyte is a polymer bearing a plurality of cationiccharges, i.e. the polyelectrolyte contains repeat units bearing cationicmoieties. Suitable cationic polyelectrolytes for use in the compositionsof the present invention contain cationic nitrogen-containing moietiessuch as quaternary ammonium or cationic protonated amino moieties. Thecationic protonated amines can be primary, secondary, or tertiary amines(preferably secondary or tertiary), depending upon the particularspecies and the selected pH of the composition. Any anionic counterionscan be used in association with the cationic polyelectrolytes so long asthe polyelectrolytes remain soluble in water, in the composition, or ina coacervate phase of the composition, and so long as the counterionsare physically and chemically compatible with the essential componentsof the composition or do not otherwise unduly impair productperformance, stability or aesthetics. Non limiting examples of suchcounterions include halides (e.g., chloride, fluoride, bromide, iodide),sulfate, methylsulfate, and ethylsulfate, citrate, acetate, and lactate.

Compositions of the present invention contain from about 0.1 wt % toabout 1 wt % cationic polyelectrolyte, more preferably from about 0.1 wt% to about 0.8 wt %.

Preferred cationic polyelectrolytes used in the compositions of thepresent invention have cationic charge densities of at least about 0.2meq/g, preferably at least about 0.6 meq/g, more preferably at leastabout 1.5 meq/g, but also preferably less than about 7 meq/g, morepreferably less than about 5 meq/g, and even more preferably less thanabout 3 meq/g, at a pH range intended for use of the composition. The“cationic charge density” of a polyelectrolyte, as that term is usedherein, refers to the ratio of the number of positive charges on thepolyelectrolyte to the molecular weight of the polyelectrolyte. Theweight average molecular weight (Mw) of such suitable cationicpolyelectrolytes will generally be between about 10,000 and about 5million g/mol, preferably between about 50,000 and about 5 milliong/mol, more preferably between about 100,000 and about 3 million g/mol.The cationic polyelectrolyte may be a crosslinked (co)polymer.

Non limiting examples of such cationic polyelectrolytes are describedunder the appropriate INCI monographs in the International CosmeticIngredient Dictionary and Handbook, 15^(th) Edition published by thePersonal Care Products Council (PCPC), Washington D.C., the contents ofwhich is incorporated herein by reference.

Non limiting examples of suitable cationic polyelectrolytes includecopolymers of ethylenically unsaturated monomers having cationicprotonated amine or quaternary ammonium functionalities with watersoluble spacer monomers such as acrylamide, methacrylamide, alkyl anddialkyl acrylamides, alkyl and dialkyl methacrylamides, alkyl acrylate,alkyl methacrylate, vinyl caprolactone or vinyl pyrrolidone.

Suitable cationic protonated amino and quaternary ammonium monomers, forinclusion in the cationic polyelectrolytes of the composition herein,include ethylenically unsaturated compounds substituted withdialkylaminoalkyl acrylate, dialkylaminoalkyl methacrylate,monoalkylaminoalkyl acrylate, monoalkylaminoalkyl methacrylate, trialkylmethacryloxyalkyl ammonium salt, trialkyl acryloxyalkyl ammonium salt,diallyl quaternary ammonium salts, and vinyl quaternary ammoniummonomers having cyclic cationic nitrogen-containing rings such aspyridinium, imidazolium, and quaternized pyrrolidone, e.g., alkyl vinylimidazolium, alkyl vinyl pyridinium, alkyl vinyl pyrrolidone salts.

Other suitable cationic polyelectrolytes for use in the compositionsinclude copolymers of 1-vinyl-2-pyrrolidone and1-vinyl-3-methylimidazolium salt (e.g. chloride salt) (INCI name:Polyquaternium-16); copolymers of 1-vinyl-2-pyrrolidone anddimethylaminoethyl methacrylate (INCI name: Polyquaternium-11),copolymers of vinylpyrrolidone and quaternized vinylimidazolium salts(INCI name: Polyquaternium-44); copolymers of vinylpyrrolidone andmethacryl amidopropyltrimethyl ammonium chloride (INCI name:Polyquaternium-28); copolymers of methacryloyloxyethyl trimethylammonium methylsulfate (METAMS) and acrylamide (INCI name:Polyquaternium-5); cationic diallyl quaternary ammonium-containingpolymers, including, for example, dimethyldiallylammonium chloridehomopolymer, copolymers of acrylamide and dimethyldiallylammoniumchloride (INCI name: Polyquaternium-6 and Polyquaternium-7,respectively), amphoteric copolymers of acrylic acid includingcopolymers of acrylic acid and dimethyldiallylammonium chloride (INCIname: Polyquaternium-22), polyampholyte (co)polymers such aspolybetaines and polysulfobetaines, terpolymers of acrylic acid withdimethyldiallylammonium chloride and acrylamide (INCI name:Polyquaternium-39), and terpolymers of acrylic acid withmethacrylamidopropyl trimethylammonium chloride and methylacrylate (INCIname: Polyquaternium-47). Preferred cationic substituted monomers arethe cationic substituted dialkylaminoalkyl acrylamides,dialkylaminoalkyl methacrylamides, and combinations thereof. Anon-limiting specific example is Polymethyacrylamidopropyl TrimoniumChloride. Also preferred are copolymers of the cationic monomer withnonionic monomers such that the charge density of the total copolymersis about 0.6 to about 5 meq/gram.

Other suitable cationic polyelectrolytes for use in the compositioninclude polysaccharide polymers, such as cationic cellulose derivativesand cationic starch derivatives. Suitable cationic polysaccharidepolymers include those which conform to the formula:

wherein A is an anhydroglucose residual group, such as a starch orcellulose anhydroglucose residual; R is an alkylene oxyalkylene,polyoxyalkylene, or hydroxyalkylene group, or combination thereof; R1,R2, and R3 independently are alkyl, aryl, alkylaryl, arylalkyl,alkoxyalkyl, or alkoxyaryl groups, each group containing up to about 18carbon atoms, and the total number of carbon atoms for each cationicmoiety (i.e., the sum of carbon atoms in R1, R2 and R3) preferably beingabout 20 or less, more preferably about 10 or less; and X is an anioniccounterion as described in hereinbefore. In one preferred embodiment, Ris 2-hydroxypropyl and R₁, R₂, and R₃ are methyl.

Preferred cationic cellulose polymers are salts of hydroxyethylcellulose reacted with trimethyl ammonium substituted epoxide (INCIname: Polyquaternium-10). Other suitable types of cationic celluloseinclude the polymeric quaternary ammonium salts of hydroxyethylcellulose reacted with lauryl dimethyl ammonium-substituted epoxide(INCI name: Polyquaternium-24) and reacted with lauryl dimethylammonium-and trimethylammonium-substituted epoxide (INCI name:Polyquaternium-67).

Other suitable cationic polyelectrolytes include cationic galactomannanssuch as cationic tara gum, cassia gum and guar gum derivatives, such asGuar Hydroxypropyltrimonium Chloride, specific examples of which includethe Jaguar series commercially available from Solvay, Inc. and theN-Hance series commercially available from Ashland, Inc. Other suitablecationic polyelectrolytes include quaternary nitrogen-containingcellulose ethers, some examples of which are described in U.S. Pat. No.3,962,418, which description is incorporated herein by reference. Othersuitable cationic polyelectrolytes include copolymers of etherifiedcellulose, guar and starch, some examples of which are described in U.S.Pat. No. 3,958,581, the contents of which is incorporated herein byreference. Other suitable conditioning polymers include those disclosedin U.S. Pat. No. 5,876,705, the contents of which is incorporated hereinby reference. When used, the cationic polyelectrolytes herein are eithersoluble in the composition or are soluble in a complex coacervate phasein the composition formed by the cationic polyelectrolyte and theanionic, amphoteric and/or zwitterionic detersive surfactant componentdescribed hereinbefore.

Other suitable cationic polyelectrolytes may include proteins bearingcationic charges, like gelatin, ovalbumin, serum albumin, casein andhydrolyzed wheat or rice or silk protein substituted withhydroxypropyltrimonium moieties and cationic polypeptides, such aspoly(L-lysine), poly(L-arginine), abaecin, propenin, or indolicidin.

Other suitable cationic polyelectrolytes include linear and branchedpolyethyleneimine (PEI) (co)polymers. Examples include PEI-2500,PEI-14M.

Generally, it is recognized that the cationic polyelectrolytes exist inthe cleansing composition as a coacervate phase or form a coacervatephase upon dilution. If not already a coacervate in the cleansingcomposition, the cationic polyelectrolyte will preferably exist in acomplex coacervate form in the cleansing composition upon dilution withwater to a weight ratio of water to composition of about 20:1, morepreferably at about 10:1, even more preferably at about 5:1, and evenmore preferably at about 3:1.

Surfactants

Compositions of the present invention contain from about 1 wt % to about25 wt % surfactant, more preferably from about 3 wt % to about 25 wt %surfactant, more preferably from about 3 wt % to about 15 wt %, evenmore preferable from about 3 wt % to about 12 wt % and even morepreferably from about 4 wt % to about 12 wt %.

Suitable surfactants may be anionic, zwitterionic, nonionic and cationicsurfactants, examples of which are described below.

As used herein, the term “anionic surfactant” refers to a surfactantmolecule bearing at least a negative charge and no positive chargebesides counterion(s), M⁺. Suitable anionic surfactants include thoseselected from the following classes of surfactants:

-   -   Acyl isethionates

where RCO=C₈-C₂₀ acyl (linear or branched, saturated or unsaturated) ormixtures thereof, R′=H or CH₃, M⁺=monovalent cation, such as SodiumCocoyl Isethionate (RCO=coco acyl, R′=H, M⁺=Na⁺) and Sodium LauroylMethyl Isethionate (RCO=lauroyl, R′=CH₃, M⁺=Na⁺).

-   -   Alkyl sulfosuccinates

where R=C₈-C₂₀ alkyl (linear or branched, saturated or unsaturated) ormixtures thereof and M⁺=monovalent cation, such as Disodium LaurylSulfosuccinate (R=lauryl, M⁺=Na⁺).

-   -   α-Sulfo fatty acid esters

where R=C₆-C₁₆ alkyl (linear or branched, saturated or unsaturated) ormixtures thereof, R′=C₁-C₂ alkyl, and M⁺=monovalent cation, such asSodium Methyl 2-Sulfolaurate (R=C₁₀H₂₁, R′=methyl, CH₃, and M⁺=Na⁺);

-   -   α-Sulfo fatty acid salts

where R=C₆-C₁₆ alkyl (linear or branched, saturated or unsaturated) ormixtures thereof, M⁺=monovalent cation, such as Disodium 2-Sulfolaurate(R=C₁₀H₂₁, M⁺=Na⁺);

-   -   Alkyl sulfoacetates

where R=C₆-C₁₈ alkyl (linear or branched, saturated or unsaturated) ormixtures thereof, M⁺=monovalent cation, such as Sodium LaurylSulfoacetate (R=lauryl, C₁₂H₂₅, M⁺=Na⁺).

-   -   Alkyl sulfates

where R=C₈-C₂₀ alkyl (linear or branched, saturated or unsaturated) ormixtures thereof. Specific examples include TEA-Lauryl Sulfate(R=lauryl, C₁₂H₂₅, M⁺=⁺HN(CH₂CH₂OH)₃), Sodium Lauryl Sulfate (R=lauryl,C₁₂H₂₅, M⁺=Na⁺), and Sodium Coco-Sulfate (R=coco alkyl, M⁺=Na⁺).

-   -   Alkyl glyceryl ether sulfonates or alkoxyl hydroxypropyl        sulfonates:

where R=C₈-C₂₄ alkyl (linear or branched, saturated or unsaturated) ormixtures thereof and M⁺=monovalent cation, such as Sodium CocoglycerylEther Sulfonate (R=coco alkyl, M⁺=Na⁺);

-   -   Alpha olefin sulfonates (AOS) prepared by sulfonation of long        chain alpha olefins. Alpha olefin sulfonates consist of mixtures        of alkene sulfonates,

where R=C₄-C₁₈ alkyl or mixtures thereof and M⁺=monovalent cation, andhydroxyalkyl sulfonates,

where R=C₄-C₁₈ alkyl or mixtures thereof and M⁺=monovalent cation.Examples include Sodium C12-14 Olefin Sulfonate (R=C₈-C₁₀ alkyl, M⁺=Na⁺)and Sodium C14-16 Olefin Sulfonate (R=C₁₀-C₁₂ alkyl, M⁺=Na⁺);

-   -   Alkyl sulfonates or paraffin sulfonates:

where R=C₈-C₂₄ alkyl (linear or branched, saturated or unsaturated) ormixtures thereof and M⁺=monovalent cation. Examples include SodiumC13-17 Alkane Sulfonate (R=C₁₃-C₁₇ alkyl, M⁺=Na⁺) and Sodium C14-17Alkyl Sec Sulfonate (R=C₁₄-C₁₇ alkyl, M⁺=Na⁺);

-   -   Alkylaryl sulfonates or linear alkyl benzene sulfonates

where R=C₆-C₁₈ alkyl (linear, saturated or unsaturated) or mixturesthereof and M⁺=monovalent cation. Examples include SodiumDeceylbenzenesulfonate (R=C₁₀ alkyl, M⁺=Na⁺) and AmmoniumDodecylbenzensulfonate (R=C₁₂ alkyl, M⁺=NH₄ ⁺);

-   -   Alkyl ether sulfates

where R=C₈-C₂₄ alkyl (linear or branched, saturated or unsaturated) ormixtures thereof, n=1-12, and M⁺=monovalent cation. Examples includeSodium Laureth Sulfate (R=C₁₂ alkyl, M⁺=Na⁺, n=1-3), Ammonium LaurethSulfate (R=C₁₂ alkyl, M⁺=NH₄ ⁻, n=1-3), and Sodium Trideceth Sulfate(R=C₁₃ alkyl, M⁺=Na⁺, n=1-4);

-   -   Alkyl monoglyceride sulfates

where RCO=C₈-C₂₄ acyl (linear or branched, saturated or unsaturated) ormixtures thereof and M⁺=monovalent cation. Examples include SodiumCocomonoglyceride Sulfate (RCO=coco acyl, M⁺=Na⁺) and AmmoniumCocomonoglyceride Sulfate (RCO=coco acyl, M⁺=NH₄ ⁺);

-   -   Alkyl ether carboxylates

where R=C₈-C₂₄ alkyl (linear or branched, saturated or unsaturated) ormixtures thereof, n=1-20, and M⁺=monovalent cation. Examples includeSodium Laureth-13 Carboxylate (R=C₁₂ alkyl, M⁺=Na⁺, n=13), and SodiumLaureth-3 Carboxylate (R=C₁₂ alkyl, M⁺=Na⁺, n=3);

-   -   Alkyl ether sulfosuccinates

where R=C₈-C₂₀ alkyl (linear or branched, saturated or unsaturated) ormixtures thereof, n=1-12, and M⁺=monovalent cation, such as DisodiumLaureth Sulfosuccinate (R=lauryl, n=1-4, and M⁺=Na⁺)

-   -   Dialkyl sulfosuccinates

where R=C₆-C₂₀ alkyl (linear or branched, saturated or unsaturated) ormixtures thereof and M⁺=monovalent cation, such as Diethylhexyl SodiumSulfosuccinate (R=2-ethylhexyl, M⁺=Na⁺).

-   -   Alkylamidoalkyl sulfosuccinates

where R=C₈-C₂₀ alkyl (linear or branched, saturated or unsaturated) ormixtures thereof, R′=C₂-C₄ alkyl (linear or branched), and M⁺=monovalentcation, such as Disodium Cocamido MIPA-Sulfosuccinate (RCO=coco acyl,R′=isopropyl, M⁺=Na⁺).

-   -   Alkyl sulfosuccinamates

where R=C₈-C₂₀ alkyl (linear or branched, saturated or unsaturated) ormixtures thereof and M⁺=monovalent cation, such as Disodium StearylSulfosuccinamate (R=stearyl, C₁₈H₃₇, M⁺=Na⁺).

-   -   Acyl glutamates

where RCO=C₆-C₂₀ acyl (linear or branched, saturated or unsaturated) ormixtures thereof, R′=H or CH₃, M⁺=monovalent cation, such as DisodiumCocoyl Glutamate (RCO=coco acyl, R′=H, M⁺=Na⁺) and Disodium LauroylGlutamate (RCO=lauroyl, R′=H, M⁺=Na⁺).

-   -   Acyl aspartates

where RCO=C₆-C₂₀ acyl (linear or branched, saturated or unsaturated) ormixtures thereof, R′=H or CH₃, M⁺=monovalent cation, such as DisodiumN-Lauroyl Aspartate (RCO=lauroyl, R′=H, M⁺=Na⁺).

-   -   Acyl taurates

where RCO=C₆-C₂₀ acyl (linear or branched, saturated or unsaturated) ormixtures thereof, R′=H or CH₃, M⁺=monovalent cation, such as SodiumMethyl Cocoyl Taurate (RCO=coco acyl, R′=CH₃, M⁺=Na⁺) and Sodium CocoylTaurate (RCO=lauroyl, R′=H, M⁺=Na⁺).

-   -   Acyl lactylates

where RCO=C₈-C₂₀ acyl (linear or branched, saturated or unsaturated) ormixtures thereof, M⁺=monovalent cation, such as Sodium Lauroyl Lactylate(RCO=lauroyl, M⁺=Na⁺).

-   -   Acyl glycinates and acyl sarcosinates

where RCO=C₈-C₂₀ acyl (linear or branched, saturated or unsaturated) ormixtures thereof, R′=H (glycinate) or CH₃ (sarcosinate), M⁺=monovalentcation, such as Sodium Cocoyl Glycinate (RCO=coco acyl, R′=H, M⁺=Na⁺),Ammonium Cocoyl Sarcosinate (RCO=coco acyl, R′=CH₃, M⁺=NH₄) and SodiumLauroyl Sarcosinate (RCO=lauroyl, R′=CH₃, M⁺=Na⁺).

-   -   Anionic derivatives of alkyl polyglucosides, including: Sodium        Lauryl Glucoside Carboxylate, Disodium Coco-Glucoside Citrate,        Sodium Coco-Glucoside Tartrate, Disodium Coco-Glucoside        Sulfosuccinate; Sodium Cocoglucosides Hydroxypropylsulfonate,        Sodium Decylglucosides Hydroxypropylsulfonate, Sodium        Laurylglucosides Hydroxypropylsulfonate; Sodium        Hydroxypropylsulfonate Cocoglucoside Crosspolymer, Sodium        Hydroxypropylsulfonate Decylglucoside Crosspolymer, Sodium        Hydroxypropylsulfonate Laurylglucoside Crosspolymer; Anionic        polymeric APG derivatives, such as those described in O'Lenick,        U.S. Pat. Nos. 7,507,399; 7,375,064; and 7,335,627; and        combinations of two or more thereof, and the like.

As used herein, the term “sulfated anionic surfactant” refers to anionicsurfactants containing a —SO₄ ⁻M⁺ group, with M⁺ being absent, or H⁺ orNH₄ ⁺ or Na⁺ or K⁺ or other monovalent or multivalent anion. Examples ofsulfated anionic surfactants include, but are not limited to, sodiumlauryl sulfate and sodium laureth sulfate. In certain embodiments, thecompositions of the present invention are essentially free of sulfatedanionic surfactant, and preferably are free of sulfated anionicsurfactant.

In certain embodiments, the compositions of the present invention areessentially free of anionic surfactant, and preferably are free ofanionic surfactant.

In certain embodiments of the present invention, the composition maycomprise a zwitterionic surfactant. Suitable concentrations ofzwitterionic surfactant are from about 0 wt % to 15 wt %, preferablyfrom about 1-10 wt %, more preferably from about 2 wt % to 6 wt %.

In certain embodiments, the compositions of the present inventioncontain one or more anionic and one or more zwitterionic surfactant(s).Ratios of the weight of the anionic to the zwitterionic surfactant(s) inthe composition can range from 1:0 to 0:1. Typical ranges areanionic:zwitterionic 4:1 to 1:4.

As used herein, “zwitterionic surfactant” refers to an amphiphilicmolecule comprising a hydrophobic group and one or more hydrophilicgroups comprising two moieties of opposite formal charges, or capable ofbearing opposite formal charges (as a function of acid-base propertiesand solution pH). Sometimes such surfactants are also referred to as“amphoteric surfactants”.

Suitable zwitterionic surfactants include, but are not limited to,surfactants described by formulas:

where R₁ is a linear, branched, saturated or unsaturated C5 to C21hydrophobe;R₂ is a linear, branched, or cyclic alkyl, hydroxyalkyl, or aromaticgroup;R₃ is a linear or branched alkyl, hydroxyalkyl, or aromatic group;R₄ is a linear or branched alkyl, hydroxyalkyl, or aromatic group;R₅ is a linear or branched alkyl, hydroxyalkyl, or aromatic group; andany of R₂, R₄, or R₅ can by linked in a cyclic structure; and

Y is —N(H)—, —N(R3)-, —O—, —S—; and

X is —CO2-, —SO3-, or —SO4- or phosphate or phosphonate.

Examples of zwitterionic surfactants include:

-   -   Alkylamidoalkyl betaines of the formula:

where RCO=C₆-C₂₄ acyl (saturated or unsaturated) or mixtures thereof andx=1-4. Examples include cocamidoethyl betaine (RCO=coco acyl, x=2),cocamidopropyl betaine (RCO=coco acyl, x=3), lauramidopropyl betaine(RCO=lauroyl, and x=3), myristamidopropyl betaine (RCO=myristoyl, andx=3), soyamidopropyl betaine (R=soy acyl, x=3), and oleamidopropylbetaine (RCO=oleoyl, and x=3).

-   -   Alkylamidoalkyl hydroxysultaines of the formula:

where RCO=C₆-C₂₄ acyl (saturated or unsaturated) or mixtures thereof.Examples include cocamidopropyl hydroxysultaine (RCO=coco acyl, x=3),lauramidopropyl hydroxysultaine (RCO=lauroyl, and x=3),myristamidopropyl hydroxysultaine (RCO=myristoyl, and x=3), andoleamidopropyl hydroxysultaine (RCO=oleoyl, and x=3).

-   -   Alkylamidoalkyl sultaines of the formula:

where RCO=C₆-C₂₄ acyl (saturated or unsaturated) or mixtures thereof.Examples include cocamidopropyl sultaine (RCO=coco acyl, x=3),lauramidopropyl sultaine (RCO=lauroyl, and x=3), myristamidopropylsultaine (RCO=myristoyl, and x=3), soyamidopropyl betaine (RCO=soy acyl,x=3), and oleamidopropyl betaine (RCO=oleoyl, and x=3).

-   -   Amphoacetates of the formula:

where RCO=C₆-C₂₄ acyl (saturated or unsaturated) or mixtures thereof andM⁺=monovalent cation. Examples include sodium lauroamphoacetate(RCO=lauroyl and M⁺=Na⁺) and sodium cocoamphoacetate (RCO=coco acyl andM⁺=Na⁺).

-   -   Amphodiacetates of the formula:

where RCO=C₆-C₂₄ acyl (saturated or unsaturated) or mixtures thereof andM⁺=monovalent cation. Examples include disodium lauroamphodiacetate(RCO=lauroyl and M=Na⁺) and disodium cocoamphodiacetate (RCO=coco acyland M⁺=Na⁺).

-   -   Amphopropionates of the formula:

where RCO=C₆-C₂₄ acyl (saturated or unsaturated) or mixtures thereof andM⁺=monovalent cation. Examples include sodium lauroamphopropionate(RCO=lauroyl and M⁺=Na⁺) and sodium cocoamphopropionate (RCO=coco acyland M⁺=Na⁺).

-   -   Amphodipropionates of the formula:

where RCO=C₆-C₂₄ acyl (saturated or unsaturated) or mixtures thereof andM⁺=monovalent cation. Examples include disodium lauroamphodipropionate(RCO=lauroyl and M⁺=Na⁺) and disodium cocoamphodipropionate (RCO=cocoacyl and M⁺=Na⁺).

-   -   Amphohydroxypropylsulfonates of the formula:

where RCO=C₆-C₂₄ acyl (saturated or unsaturated) or mixtures thereof andM⁺=monovalent cation, such as sodium lauroamphohydroxypropylsulfonate(RCO=lauroyl and M⁺=Na⁺) and sodium cocoamphohydroxypropylsulfonate(RCO=coco acyl and M⁺=Na⁺).

Other examples include amphohydroxyalkylphosphates and alkylamidoalkylamine oxides.

In certain embodiments of the present invention, the composition maycomprise a nonionic surfactant. Suitable concentrations of nonionicsurfactant are from about 0 wt % to about 15 wt %, typically from about1-10 wt %, more typically from about 2 wt % to about 6 wt %. As usedherein, the term “nonionic surfactant” refers to a surfactant moleculebearing no electrostatic charge. Any of a variety of nonionicsurfactants is suitable for use in the present invention. Examples ofsuitable nonionic surfactants include, but are not limited to, fattyalcohol, acid, or amide ethoxylates, monoglyceride ethoxylates, sorbitanester ethoxylates, alkyl polyglucosides, mixtures thereof, and the like.Certain preferred nonionic surfactants include polyethyleneoxyderivatives of polyol esters, wherein the polyethyleneoxy derivative ofpolyol ester (1) is derived from (a) a fatty acid containing from about8 to about 22, and preferably from about 10 to about 14 carbon atoms,and (b) a polyol selected from sorbitol, sorbitan, glucose, α-methylglucoside, polyglucose having an average of about 1 to about 3 glucoseresidues per molecule, glycerine, pentaerythritol and mixtures thereof,(2) contains an average of from about 10 to about 120, and preferablyabout 20 to about 80 ethyleneoxy units; and (3) has an average of about1 to about 3 fatty acid residues per mole of polyethyleneoxy derivativeof polyol ester. Examples of such preferred polyethyleneoxy derivativesof polyol esters include, but are not limited to PEG-80 sorbitan laurateand Polysorbate 20. PEG-80 Sorbitan Laurate is a sorbitan monoester oflauric acid ethoxylated with an average of about 80 moles of ethyleneoxide. Polysorbate 20 is the laurate monoester of a mixture of sorbitoland sorbitol anhydrides condensed with approximately 20 moles ofethylene oxide.

Another class of suitable nonionic surfactants includes long chain alkylglucosides or polyglucosides, which are the condensation products of (a)a long chain alcohol containing from about 6 to about 22, and preferablyfrom about 8 to about 14 carbon atoms, with (b) glucose or aglucose-containing polymer. Preferred alkyl glucosides comprise fromabout 1 to about 6 glucose residues per molecule of alkyl glucoside. Apreferred glucoside is Decyl Glucoside, which is the condensationproduct of decyl alcohol with a glucose oligomer.

Another class of suitable nonionic surfactants is polyglycerol nonionicsurfactants. Examples of polyglycerol nonionic surfactants include, butare not limited to, polyglycerol esters (PGEs), such as Polyglycerol-10Laurate.

As used herein, the term “polyglyceryl nonionic surfactant” means anamphiphilic molecule comprising one or more nonionic hydrophilicsegments comprised of a polyglyceryl moiety and one or more hydrophobicmoieties. Examples of polyglyceryl nonionic surfactants include, but arenot limited to, polyglyceryl esters (PGEs), such as polyglyceryl-10laurate where PG=polyglyceryl moiety comprising ten (10) glyceryl repeatunits, and R=C₁₁H₂₃:

as well as, polyglyceryl-10 caprylate/caprate, polyglyceryl-10 cocoate,polyglyceryl-10 myristate, polyglyceryl-10 palmitate, polyglyceryl-10oleate, polyglyceryl-12 laurate, and the like. PGEs of the presentinvention may include polyglyceryl moieties bearing multiple estersubstitutions (i.e. the PGEs may be monoesters, diesters, triesters,etc.). Other polyglyceryl nonionic surfactants include polyglycerylethers, such as polyglyceryl-10 lauryl ether, where PG=polyglycerylmoiety comprising 10 glyceryl repeat units, and R=C₁₂H₂₅:

and the like. Still other polyglyceryl nonionic surfactants includepolyglyceryl sorbitan fatty acid esters, such as polyglyceryl-20sorbitan laurate, where PG=polyglycerol, the sum of all PG RUs=20, andR=C₁₁H₂₃. (see Bevinakatti, et al. WO 2009016375, assigned to CrodaInternational PLC)

Another class of suitable nonionic surfactants includes alkanolamides,like cocamide MEA and cocamide DEA.

In certain embodiments of the present invention, the composition mayfurther comprise an inorganic salt. Inorganic salts that are suitablefor use in this invention include, but are not limited to, sodiumchloride, potassium chloride, sodium bromide, potassium bromide,ammonium chloride, ammonium bromide and other mono-valent as well asmulti-valent ion containing salts. Typically, compositions of thepresent invention will comprise from about 0.05 wt % to about 6 wt % ofinorganic salt, or from about 0.1 wt % to about 4 wt % of inorganicsalt, or from about 0.1 wt % to about 2 wt % of inorganic salt, or fromabout 0.1 wt % to about 1.5 wt % of inorganic salt.

In certain embodiments of the present invention, the composition mayfurther comprise a cationic surfactant. Classes of cationic surfactantsthat are suitable for use in this invention include, but are not limitedto, alkyl quaternaries (mono, di, or tri), benzyl quaternaries, esterquaternaries, ethoxylated quaternaries, alkyl amines, and mixturesthereof, wherein the alkyl group has from about 6 carbon atoms to about30 carbon atoms, with about 8 to about 22 carbon atoms being preferred.

The composition of this invention may further contain any otheringredients or additives typically used in personal care products, e.g.dermatological or in cosmetic formulations, including activeingredients. Examples of further ingredients or additives aresurfactants, emulsifiers, viscosity controlling agents, lubricants,chelating agents, fillers, binding agents, anti-oxidants, preservativesand preservative boosters, dyes, buffering agents, pH adjusters,solvents, and benefit agents such as active ingredients, fragrances,exfoliates, emollients, moisturizers, humectants, pigments andopacifying agents, and the like, provided that they are physically andchemically compatible with the other components of the composition.Active ingredients may include, without limitation, anti-inflammatoryagents, anti-bacterials, anti-fungals, anti-itching agents, moisturizingagents, plant extracts, vitamins, and the like. Also included aresunscreen actives which may be inorganic or organic in nature.

The composition of this invention may further contain thickeners,suspending agents, and rheology modifiers, which are not part of the“Polyelectrolyte Conditioning System”. Examples include, but are notlimited to, a) naturally-derived polysaccharides including Cyamopsistetragonoloba (guar) gum, cassia gum, microcrystalline cellulose,ethoxylated and nonethoxylated derivatives of cellulose (e.g.,hydroxyethyl and hydroxypropyl methylcellulose, etc.), and hydroxypropylguar, b) synthetic polymers including acrylate polymers such assurfactant responsive microgels (as described e.g. in U.S. Pat. No.9,096,755 B2, examples include Acrylates/Beheneth-25 Methacrylate/HEMACrosspolymer and Acrylates/Beheneth-25 Methacrylate/HEMA Crosspolymer-2)and Acrylates/Aminoacrylates/C10-30 Alkyl PEG-20 Itaconate Copolymer, c)micellar thickeners, such as cocamide MIPA, lauryl lactyl lactate, orsorbitan sesquicaprylate, or polyethylene glycol-based thickeners suchas PEG-150 Distearate and PEG-120 Methyl Glucose Dioleate and Trioleate,and d) other thickeners like silicones, waxes, clays, silicas, salts,natural and synthetic esters, or fatty alcohols, and e) combinations oftwo or more thereof and the like.

Examples of preservatives and preservative boosters include but are notlimited to organic acids (like e.g., benzoic acid, lactic acid,salicylic acid), benzyl alcohol, caprylyl glycol, decylene glycol,ethylhexylglycerin, gluconolactone, methylisothazolinone, andcombinations of two or more thereof, and the like.

The composition of the present invention may include dispersed insolubleparticles. The dispersed particles may be benefit agents, such as oildroplets, zinc pyrithione particles, mica particles, colloidal oatmeal,and crushed walnut shells. In the compositions of the present invention,it is preferable to incorporate at least 0.025 wt % of the dispersedparticles, more preferably at least 0.05 wt %, still more preferably atleast 0.1 wt %, even more preferably at least 0.25 wt %, and yet morepreferably at least 0.5 wt % of the dispersed particles. In thecompositions of the present invention, it is preferable to incorporateno more than about 30 wt % of the dispersed particles, more preferablyno more than about 15 wt %, and even more preferably no more than 10 wt%.

The pH of compositions of the present invention is adjusted topreferably from about 3 to about 7, more preferably from about 3 toabout 6.5, more preferably from about 3 to about 6, more preferably fromabout 3 to about 5.5, more preferably from about 3 to about 5, and mostpreferably from about 3 to about 4.5. The pH of the composition may beadjusted as low as 3 provided that formula stability and performance(e.g., foaming, mildness and viscosity) are not negatively affected. ThepH of the composition may be adjusted to the appropriate acidic valueusing any cosmetically acceptable organic or inorganic acid, such ascitric acid, acetic acid, glycolic acid, lactic acid, malic acid,tartaric acid, hydrochloric acid, combinations of two or more thereof orthe like.

EXAMPLES

The following examples are meant to illustrate the present invention,not to limit it thereto.Test methods used in the Examples are described as follows:

Dry Precipitate Mass Yield Test:

Measurements of coacervate precipitation in diluted cleansingcompositions were made using the following procedure. First, 2.5 g ofcleansing composition were added to a 20 mL glass scintillation vialcontaining 7.5 g of DI water. The vial was closed, and mixed on a VWRAnalog vortex mixer for 20 seconds. Immediately after mixing, lmL of thebulk dilute solution was pipetted into a 1.5 mL microcentrifuge tube andpreweighed on a Mettler Toledo XS105 Analytical Balance. After the massof the centrifuge tube with 1 mL of solution was measured, the tube wascentrifuged in a VWR Galaxy Micro-centrifuge at 13,000 rpm. Aftercentrifugation, if a visible precipitate was observed, the supernatantwas removed via pipette, leaving only the polyelectrolyte-richprecipitate. The centrifuge tube was then placed in a 50° C. ovenovernight, with the cap open, to remove water from the precipitate. Thecentrifuge tube was then reweighed with only the dry precipitate. Themass of total dilute solution and dry precipitate was then calculated bysubtracting out the centrifuge tube mass from respective measurements ofthe centrifuge tube with 1 mL of dilution solution and dry precipitate.

The Dry Precipitate Mass Yield was calculated as the ratio of dryprecipitate mass to the total mass of cationic and anionicpolyelectrolytes contained in the dilute solution added to themicrocentrifuge tube. In some cases, rather than a solid/viscousprecipitate appearing at the bottom of the tube, a single phase wasobserved. These samples were denoted as exhibiting a single phase upondilution/centrifugation, and the Dry Precipitate Mass Yield is recordedas 0.

Viscosity Tests and Significant Viscosity Change Criteria:

Determinations of apparent viscosity of the cleansing compositions wereconducted on a controlled-stress rheometer (AR-2000, TA InstrumentsLtd., New Castle, Del., USA). Steady-state shear rate sweeps wereperformed at 25.0±0.1° C. using a cone-plate geometry (50 mm diameter,1° cone angle). Data acquisition and analysis were performed with theRheology Advantage software v5.7.0 (TA Instruments Ltd., New Castle,Del., USA). Mid-shear viscosities are taken from steady-state flowmeasurements at a shear rate of 10 s⁻¹, and are given in centiPoise(cps). Low-shear viscosities are taken from steady-state flowmeasurements at a shear rate of 1 s⁻¹, and are given in centiPoise(cps).

As used herein, a minimum significant-change-threshold is defined asΔη_(min)=82.65×η^(0.396), where r is the viscosity measured using theprotocol described above. This relationship between detectable viscositydifferences is consistent with qualitative observations, values from theliterature, and general predictions for power-law relationships betweenphysical values and perceived magnitudes (Bergmann Tiest, W. M., VisionResearch, 109, 2015, 178-184, Bergmann Tiest et al., IEEE Transactionson Haptics, 6, 2013, 24-34, Stevens, J. C. & Guirao, M., Science, 144,1964, 1157-1158). Then, in cases where a polyelectrolyte is added to acomposition with viscosity η₀, we define the minimum viscosity necessaryto claim an observable/noticeable change in viscosity asη_(min)=Δη_(min)+η₀=82.65×η₀ ^(0.396)+η₀.

Yield Stress Test:

As used herein, the term “yield stress” indicates that a viscoelasticmaterial/sample possesses solid-dominated behavior. In other words, theelastic modulus must be higher than the viscous modulus in the lowstrain/stress plateau region of the amplitude sweep. The yield stressvalue is then taken as the stress at the crossover of the storagemodulus G′ and the loss modulus G″ (G′=G″) and expressed in Pascal (Pa).

The cleansing compositions of the present invention exhibitsubstantially no yield stress value associated with or attributable tothe Polyelectrolyte Conditioning System. That is, the compositions donot contain anionic polyelectrolytes in the Polyelectrolyte ConditioningSystem in an amount sufficient to provide the composition withmeasurable yield stress or increase in yield stress value, as determinedby the method described herein. A measurable increase in yield stressvalue is typically about 0.01 Pa or more, or even more typically about0.05 Pa or more, or even more typically about 0.1 Pa or more.

Determinations of the yield stress value of the cleansing compositionswere conducted on a controlled-stress rheometer (AR-2000, TA InstrumentsLtd., New Castle, Del., USA). Oscillatory strain amplitude sweeps from0.1%-1000% were performed at 25.0±0.1° C. using a cone-plate geometry(50 mm diameter, 1° cone angle) at an oscillation frequency of 1 rad/s.Data acquisition and analysis were performed with the Rheology Advantagesoftware v5.7.0 (TA Instruments Ltd., New Castle, Del., USA). The yieldstress value is taken as the oscillatory stress below which the storagemodulus G′ exceeds the loss modulus G″, and above which G″ exceeds G′.In cases where G′ does not exceed G″ at any oscillatory stress above thesensitivity of the instrument, the yield stress value is denoted as 0Pa. Except otherwise stated, yield stress values are given in Pascal(Pa).

Ellipsometry-Based Polyelectrolyte Deposition Test:

Evaluations of polyelectrolyte deposition efficacy of Comparative andInventive Examples during cleansing were conducted on a model surfaceand measured using ellipsometry. First, 2.5 g of cleansing compositionwere added to a 20 mL glass scintillation vial containing 7.5 g of DIwater heated to 40° C. The vial was closed, and stirred on a VWR Analogvortex mixer for 20 seconds. Immediately after stirring, 100 μL of thedilute solution were pipetted onto a 2 cm×2 cm cut chip of test-gradesilicon wafer (University Wafer) (previously cleaned with deionized (DI)water and ethanol and dried), spread over the surface, and allowed tosit for 30 seconds. After tipping the silicon wafer at ˜45°, 5 mL of DIwater at 40° C. was dripped over the silicon chip, rinsing the dilutecleansing solution from the surface. The chip was then gently dabbedwith a wipe and allowed to dry for 3-4 minutes.

The thickness of deposit on the silicon wafer was measured on analpha-SE Spectroscopic Ellipsometer (J. A. Woolam Co., Inc) at 5different locations on each chip before and after treatment with thecleansing solution. The layer thickness is calculated by applying astandard fit to the raw ellipsometeric data for a transparent film on asilicon substrate, using the CompleteEASE® software package. The finalaverage deposited layer thickness is then calculated by subtracting theaverage layer thickness measured before applying the dilute compositionfrom the average layer thickness measured after applying the dilutecomposition.

Dimethicone Deposition Test:

Evaluations of silicone deposition efficacy on skin from Inventive andComparative Examples were conducted on a human volunteer's forearm andmeasured using attenuated total reflectance fourier transform infraredspectroscopy (ATR-FTIR), similar to previous evaluations performed forsilicone on human skin (Klimisch, H. M. & G. Chandra, J. Soc. Cosmet.Chem., 37, 1986, 73-87). ATR-FTIR measurements were taken using aREMSPEC IR TissueView™ ATR FTIR spectrometer. Acquired spectra weretaken over a wave number range of 900 cm⁻¹ to 3500 cm⁻¹ at 2 cm⁻¹intervals.

Dimethicone-containing formulations of Inventive and ComparativeExamples were made by incorporating a sufficient quantity of apre-emulsified dimethicone which has a dimethicone droplet size of about0.65 μm to a formulation to obtain 5 wt % active dimethicone in thefinished formulation. For example, 0.78 g of Xiameter MEM-1352 (64 wt %active dimethicone) was added to 9.22 g of formulation, for a total of0.5 g dimethicone in 10.0 g of formulation.

The volar forearm of the subject was first washed with a cleansingcomposition comprised of Sodium Laureth Sulfate (SLES, 5 wt % active),Cocamidopropyl Betaine (CAPB, 5 wt % active), NaCl and Sodium Benzoate,adjusted to pH of 4.5, and thoroughly rinsed and dried with a sterilewipe. A 5 cm×7 cm rectangular area was then marked on the volar forearm.An ATR-FTIR spectrum was then acquired at the center of the marked area.Then, 100 μL of dimethicone-containing formulation and 100 μL of DIwater were applied to the marked area of the forearm, and gently rubbedover the area with a gloved index finger and forefinger for 30 seconds.After the formulation was allowed to sit on the arm for an additional 30seconds, the forearm was placed 6 inches under a stream (flow rate of 3liters per minute) of 37° C. water from a spray faucet (with the centerof the spray centered at the centered of the marked area) for 10seconds. After rinsing, the arm was shaken briefly, the arm outside themarked area was dried with a sterile wipe, and the marked area wasallowed to air dry (5-10 minutes). After drying, an ATR-FTIR spectrumfrom 900 cm⁻¹ to 3500 cm⁻¹ was then acquired at the center of the markedarea.

For each acquired ATR-FTIR absorbance spectrum, after respectivebaselines are subtracted for the silicone (Si) peak (1240-1280 cm⁻¹) andthe Amide II peak (1487-1780 cm−1), the absorbance values of thesilicone peak (1240-1280 cm⁻¹) were normalized by the total area underthe Amide II peak (sum of absorbance values from 1487-1780 cm⁻¹). Then,Si peak absorbance values before washing with the silicone-containingtest formulation were subtracted from Si peak absorbance values afterwashing with the silicone-containing test formulation. The Si peakabsorbance value at 1260 cm⁻¹ is then used as a measure of relativedimethicone deposition, as it has been used in previous work as ameasure of dimethicone concentration on the skin (Klimisch, H. M. & G.Chandra, J. Soc. Cosmet. Chem., 37, 1986, 73-87).

Preparation of Inventive Examples and Comparative Examples

Inventive Examples and Comparative Examples were prepared utilizingdifferent types of formulation ingredients (i.e. raw materials fromvarious suppliers). These materials, along with INCI/material names,abbreviations, trade names and suppliers are listed below:

Anionic Surfactants:

-   -   Sodium Laureth Sulfate (SLES) was obtained from BASF as Texapon®        N70.    -   Sodium C₁₄-C₁₆ Olefin Sulfonate was obtained from Stepan as        Bio-Terge® AS-40 CG K.    -   Sodium Trideceth Sulfate was obtained from Stepan as Cedepal®        TD403 MFLD.

Zwitterionic/Amphoteric/Nonionic Surfactants:

-   -   Cocamidopropyl Betaine (CAPB) was obtained from Evonik Inc. as        Tego® Betain F50, unless otherwise specified as Tego® Betain L7V        from Evonik.    -   Coco-Betaine was obtained from Solvay as Mackam® C35    -   Cocamidopropyl Hydroxysultaine (CAPHS) was obtained from Solvay        as Mirataine® CBS.    -   PEG-80 Sorbitan Laurate was obtained from Croda as Tween-28® LQ        (AP).

Cationic (Quaternary) Conditioning Polyelectrolytes:

-   -   Polyquaternium-7 (PQ-7) was obtained from Lubrizol as Merquat®        7SPR.    -   Polyquaternium-10 (PQ-10) was obtained from Dow Chemical as        Ucare® JR-400.    -   Guar Hydroxypropyltrimonium Chloride (Cationic Guar Gum) was        obtained from Solvay Inc. as Jaguar® C500.    -   Polyquaternium-5 (PQ-5) was obtained from Lubrizol as Merquat®        5.    -   Polyquaternium-28 (PQ-28) was obtained from Ashland as        Conditioneze® NT-20.    -   Polyquaternium-44 (PQ-44) was obtained from BASF as Luviquat®        UltraCare AT-1.

Anionic Polyelectrolytes:

-   -   Potassium Acrylates Copolymer was obtained from Lubrizol, Inc.    -   Acrylates Copolymer was obtained from Lubrizol as Carbopol® Aqua        SF-1.    -   Polyacrylate-33 was obtained from Solvay as Rheomer® 33T.    -   Xanthan Gum was obtained from Vanderbilt Minerals as Vanzan® NF.    -   Carboxymethylcellulose (CMC) was obtained from Ashland as        Aqualon® CMC 7MF.    -   Sodium Polyacrylate (crosslinked) was obtained as AP 80HS from        Evonik Stockhausen.

Humectants:

-   -   Glycerin was obtained from P&G Chemicals as Moon OU Glycerin.

Chelating Agents:

-   -   Disodium EDTA was obtained from DOW as Versene® NA.    -   Tetrasodium EDTA was obtained from DOW as Versene® 100XL.

Organic Acids/Preservatives:

-   -   Sodium Benzoate, NF, FCC was obtained from Emerald Performance        Materials.    -   Phenonip XB was obtained from Clariant.    -   Quaternium-15 was obtained from DOW as Dowicil® 200.

Benefit Agents:

-   -   Sodium Glycolate was obtained from Acros Organics.    -   Pre-emulsified dimethicone was obtained as Xiameter® MEM-1352        from Dow    -   Corning.

Other:

-   -   Hexylene Glycol was obtained from Penta International Crop.    -   Fragrance was obtained from Firmenich as Luxury 475537 F.    -   Disodium Cocoamphodiacetate was obtained from Croda as        Crodateric®    -   CDA 40-LQ-(AP).    -   Deionized water (DI water, also referred to as Water in the        Examples below) was obtained from a Millipore Direct-Q™ System        with Progard™ 2 filter.

Unless otherwise indicated, all ingredient products as received wereadded in amounts such that the compositions contain resulting weightpercent amounts of active material. For example, 3.5 wt % active ofCocamidopropyl Betaine (as given in Table 3a) corresponds to 9 wt %Tego® Betain F50, which has an activity of 39 wt %; 3.5 wt %/39 wt %=9wt %.

Preparation of Inventive Examples E1-E24 and Comparative ExamplesC1-C24, C29-C34

Inventive Examples E1-E24 and Comparative Examples C1-C24, C29-C34 wereprepared as follows: To an appropriately sized vessel equipped with ahotplate and overhead mechanical stirrer, the required amounts of DIwater and anionic polyelectrolyte were added and mixed at 200-250 rpmuntil the mixture was homogeneous. Anionic and zwitterionic/amphotericsurfactants were then added, and mixed until the solution becamehomogeneous. Then, aqueous solutions of sodium hydroxide and/or citricacid were added to adjust to the desired pH value 6.4-6.6. Uponstabilization of the pH, cationic polyelectrolyte was added to themixture. In the case of cationic polyelectrolytes already supplied asaqueous suspensions, the polyelectrolyte solution was added directly tothe mixture, slowly and drop-wise. For polyelectrolytes provided as drypowders, a 9 wt % premix of the polyelectrolyte in DI water was madefirst, then added slowly and dropwise to the mixture. Once the mixturewas homogeneous, sodium chloride and sodium benzoate was added, andagain allowed to mix until homogeneous. Then, aqueous solutions ofsodium hydroxide and/or citric acid in DI water were added at roomtemperature to adjust to the desired pH (pH 4.4-4.6, if not statedotherwise). DI water was added in q.s. to 100 wt %, and the batch wasallowed to mix until uniform before being discharged to an appropriatestorage vessel.

Example 1a Precipitation Measurements of Inventive (E₁-E3) andComparative Examples (C1-C3) Incorporating an Anionic Polyelectrolyteand Cationic Polyelectrolyte at Varying Weight Ratios

Comparative Examples C1-C3 and Inventive Examples E1-E3, listed in Table1a, along with Dry Precipitate Mass Yield (as measured in accord withthe Dry Precipitate Mass Yield Test as described herein), areformulations with identical quantities and types of surfactant (9 wt %SLES, 2 wt % CAPB), cationic polyelectrolyte (0.6 wt % PQ-10), salt andpreservative, but varying added quantities of an anionicpolyelectrolyte, specifically, Acrylates Copolymer, a well-knownrheology modifier and suspending agent. As shown in Table 1a, InventiveExamples E1-E3 exhibit a measurable increase in Dry Precipitate MassYield compared to the Comparative Example C1 containing no anionicpolyelectrolyte. On the other hand, Comparative Examples C2-C3, whichhave anionic to cationic polyelectrolyte weight ratios greater than 1.2(specifically, 1.67 and 2.5, respectively), exhibit no improvement inDry Precipitate Mass Yield compared to C1.

TABLE 1a wt % active material Material Material class C1 E1 E2 E3 C2 C3Acrylates Copolymer Anionic polyelectrolyte 0 0.1 0.3 0.6 1 1.5Polyquaternium-10 Cationic polyelectrolyte 0.6 0.6 0.6 0.6 0.6 0.6Sodium Laureth Anionic surfactant 9 9 9 9 9 9 Sulfate CocamidopropylAmphoteric/zwitterionic 2 2 2 2 2 2 Betaine surfactant Sodium ChlorideSalt 0.4 0.4 0.4 0.4 0.4 0.4 Sodium Benzoate Preservative 0.5 0.5 0.50.5 0.5 0.5 Citric Acid pH adjuster q.s. q.s. q.s. q.s. q.s. q.s. SodiumHydroxide pH adjuster q.s. q.s. q.s. q.s. q.s. q.s. Water Vehicle q.s.to q.s. to q.s. to q.s. to q.s. to q.s. to 100 wt % 100 wt % 100 wt %100 wt % 100 wt % 100 wt % Anionic polyelectrolyte/cationic 0.00 0.170.50 1.00 1.67 2.50 polyelectrolyte active weight ratio Dry PrecipitateMass Yield 0 1.47 2.85 2.24 0 0

Example 1b Precipitation Measurements of Inventive (E4-E6) andComparative Examples (C4-C6) Incorporating an Anionic Polyelectrolyteand Cationic Polyelectrolyte at Varying Weight Ratios

Comparative Examples C4-C6 and Inventive Examples E4-E6, listed in Table1b, along with Dry Precipitate Mass Yield (as measured in accord withthe Dry Precipitate Mass Yield Test as described herein), areformulations which contain the same components, but at different levelsand ratios, notably, a lower concentration of cationic polyelectrolytePQ-10 (0.2 wt %). As shown in Table 1b, Inventive Examples E4-E6 exhibita measurable increase in Dry Precipitate Mass Yield compared to theComparative Example C4 containing no anionic polyelectrolyte. On theother hand, Comparative Examples C5-C6, which have an anionic tocationic polyelectrolyte weight ratios greater than 1.2 (specifically,1.5 and 2.5, respectively), exhibit no improvement in Dry PrecipitateMass Yield compared to C4.

TABLE 1b wt % active material Material Material class C4 E4 E5 E6 C5 C6Acylates Copolymer Anionic polyelectrolyte 0 0.03 0.1 0.2 0.3 0.5Polyquaternium-10 Cationic polyelectrolyte 0.2 0.2 0.2 0.2 0.2 0.2Sodium Laureth Anionic surfactant 3.5 3.5 3.5 3.5 3.5 3.5 SulfateCocamidopropyl Amphoteric/zwitterionic 3.5 3.5 3.5 3.5 3.5 3.5 Betainesurfactant Sodium Chloride Salt 0.4 0.4 0.4 0.4 0.4 0.4 Sodium BenzoatePreservative 0.5 0.5 0.5 0.5 0.5 0.5 Citric Acid pH adjuster q.s. q.s.q.s. q.s. q.s. q.s. Sodium Hydroxide pH adjuster q.s. q.s. q.s. q.s.q.s. q.s. Water Vehicle q.s. to q.s. to q.s. to q.s. to q.s. to q.s. to100 wt % 100 wt % 100 wt % 100 wt % 100 wt % 100 wt % Anionicpolyelectrolyte/cationic 0.00 0.15 0.50 1.00 1.50 2.50 polyelectrolyteactive weight ratio Dry Precipitate Mass Yield 1.86 2.43 3.34 2.19 1.571.18

Example 2a Precipitation Measurements of Inventive (E7) and ComparativeExample (C7 and C8) Using a Synthetic Cationic Polyelectrolyte (PQ-7)

Comparative Examples C7-C8 and Inventive Example E7, listed in Table 2a,along with Dry Precipitate Mass Yield (as measured in accord with theDry Precipitate Mass Yield Test as described herein), are formulationswith identical quantities and types of surfactant (9 wt % SLES, 2 wt %CAPB), cationic polyelectrolyte (0.6 wt % PQ-7), salt and preservative,but varying added quantities of an anionic polyelectrolyte,specifically, Acrylates Copolymer. These compositions vary from thosegiven in Table 1a only by the type of cationic polyelectrolyte used (thesynthetic PQ-7, rather than the naturally-derived, cellulose-basedPQ-10). As shown in Table 2a, Inventive Example E7 exhibits a measurableincrease in Dry Precipitate Mass Yield compared to the ComparativeExample C7 containing no anionic polyelectrolyte. Comparative ExampleC8, which has an anionic to cationic polyelectrolyte weight ratiosgreater than 1.2 (specifically, 2.5), exhibits no measurable increase inDry Precipitate Mass Yield compared to the Comparative Example C7containing no anionic polyelectrolyte.

TABLE 2a wt % active material Material Material class C7 E7 C8 AcrylatesCopolymer Anionic 0 0.1 1.5 polyelectrolyte Polyquaternium-7 Cationic0.6 0.6 0.6 polyelectrolyte Sodium Laureth Sulfate Anionic surfactant 99 9 Cocamidopropyl Amphoteric/ 2 2 2 Betaine zwitterionic surfactantSodium Chloride Salt 0.4 0.4 0.4 Sodium Benzoate Preservative 0.5 0.50.5 Citric Acid pH adjuster q.s. q.s. q.s. Sodium Hydroxide pH adjusterq.s. q.s. q.s. Water Vehicle q.s. to 100 wt % q.s. to 100 wt % q.s. to100 wt % Anionic polyelectrolyte/cationic 0.00 0.17 2.50 polyelectrolyteactive weight ratio Dry Precipitate Mass Yield 0 1.08 0

Examples 3a-b Precipitation Measurements of Inventive (E8-E9) andComparative Examples (C9-C12) with Varying Surfactant Concentrations,Ratios and Chemistries

Comparative Examples C9-C12 and Inventive Examples E8-E9, listed inTable 3a-3b, along with Dry Precipitate Mass Yield (as measured inaccord with the Dry Precipitate Mass Yield Test as described herein),are formulations which replicate select cationic polyelectrolyte,anionic polyelectrolyte, salt and preservative levels from Table 1a and2a, but use a lower total concentration of surfactant (7 wt % total),and a different weight ratio of anionic to zwitterionic surfactant (1:1SLES:CAPB). As shown in Tables 3a and 3b, Inventive Examples E8 and E9,which have anionic to cationic polyelectrolyte weight ratios of 0.17,exhibit measurable increases in Dry Precipitate Mass Yield compared totheir corresponding Comparative Examples containing no anionicpolyelectrolyte, C9 and C11, respectively. Comparative Examples C10 andC12, which have an anionic to cationic polyelectrolyte weight ratio of2.5, exhibit no measurable increases in Dry Precipitate Mass Yieldcompared to their corresponding Comparative Examples containing noanionic polyelectrolyte, C9 and C11, respectively.

TABLE 3a wt % active material Material Material class C9 E8 C10Acrylates Copolymer Anionic 0 0.1 1.5 polyelectrolyte Polyquaternium-10Cationic 0.6 0.6 0.6 polyelectrolyte Sodium Laureth Sulfate Anionicsurfactant 3.5 3.5 3.5 Cocamidopropyl Amphoteric/ 3.5 3.5 3.5 Betainezwitterionic surfactant Sodium Chloride Salt 0.4 0.4 0.4 Sodium BenzoatePreservative 0.5 0.5 0.5 Citric Acid pH adjuster q.s. q.s. q.s. SodiumHydroxide pH adjuster q.s. q.s. q.s. Water Vehicle q.s. to 100 wt % q.s.to 100 wt % q.s. to 100 wt % Anionic polyelectrolyte/cationic 0.00 0.172.50 polyelectrolyte active weight ratio Dry Precipitate Mass Yield 2.73.11 0

TABLE 3b wt % active material Material Material class C11 E9 C12Acrylates Copolymer Anionic 0 0.1 1.5 polyelectrolyte Polyquaternium-7Cationic 0.6 0.6 0.6 polyelectrolyte Sodium Laureth Sulfate Anionicsurfactant 3.5 3.5 3.5 Cocamidopropyl Amphoteric/ 3.5 3.5 3.5 Betainezwitterionic surfactant Sodium Chloride Salt 0.4 0.4 0.4 Sodium BenzoatePreservative 0.5 0.5 0.5 Citric Acid pH adjuster q.s. q.s. q.s. SodiumHydroxide pH adjuster q.s. q.s. q.s. Water Vehicle q.s. to 100 wt % q.s.to 100 wt % q.s. to 100 wt % Anionic polyelectrolyte/cationic 0.00 0.172.50 polyelectrolyte active weight ratio Dry Precipitate Mass Yield 0.371.59 0

Example 3c Precipitation Measurements of Inventive (E10) and ComparativeExamples (C13-C14) with Varying Surfactant Concentrations, Ratios andChemistries

Comparative Examples C13-C14 and Inventive Example E10, listed in Table3c, along with Dry Precipitate Mass Yield (as measured in accord withthe Dry Precipitate Mass Yield Test as described herein), areformulations which replicate select cationic polyelectrolyte, anionicpolyelectrolyte, salt and preservative levels from Table 1a and 2a, butuse different chemistries of anionic surfactant (Sodium C14-C16 OlefinSulfonate instead of SLES) and amphoteric/zwitterionic surfactant (CAPHSinstead of CAPB). As shown in Table 3c, Inventive Example E10 exhibits ameasurable increase in Dry Precipitate Mass Yield compared to itscorresponding Comparative Examples containing no anionicpolyelectrolyte, C13. Comparative Example C14, which has an anionic tocationic polyelectrolyte weight ratio of 2.5, exhibits no measurableincreases in Dry Precipitate Mass Yield compared to its correspondingComparative Examples containing no anionic polyelectrolyte, C13.

TABLE 3c wt % active material Material Material class C13 E10 C14Acylates Copolymer Anionic 0 0.1 1.5 polyelectrolyte Polyquaternium-7Cationic 0.6 0.6 0.6 polyelectrolyte Sodium C₁₄-C₁₆ Olefin Anionicsurfactant 9 9 9 Sulfonate Cocamidopropyl Amphoteric/ 2 2 2Hydroxysultaine zwitterionic surfactant Sodium Chloride Salt 0.4 0.4 0.4Sodium Benzoate Preservative 0.5 0.5 0.5 Citric Acid pH adjuster q.s.q.s. q.s. Sodium Hydroxide pH adjuster q.s. q.s. q.s. Water Vehicle q.s.to 100 wt % q.s. to 100 wt % q.s. to 100 wt % Anionicpolyelectrolyte/cationic 0.00 0.17 2.50 polyelectrolyte active weightratio Dry Precipitate Mass Yield 0 1.17 0

Examples 4a Through 4d Measurement of Inventive (E11-E14) andComparative (C15-C22) Examples Using a Variety of Synthetic andNaturally-Derived Cationic Polyelectrolytes

Comparative Examples C15-C22 and Inventive Examples E11-E14, listed inTable 4a-4d, along with Dry Precipitate Mass Yield (as measured inaccord with the Dry Precipitate Mass Yield Test as described herein),are formulations which replicate select anionic polyelectrolyte, saltand preservative levels from Table 3a, but use different chemistries ofcationic polyelectrolyte (at 0.6 wt % active), specifically, GuarHydroxypropyltrimonium Chloride, PQ-5, PQ-22, and PQ-44. As shown inTables 4a-d, Inventive Examples E11-E14 exhibit a measurable increasesin Dry Precipitate Mass Yield compared to their correspondingComparative Examples containing no anionic polyelectrolyte, C15, C17,C19 and C21, respectively. Comparative Examples C16, C18, C20, and C22,which have an anionic to cationic polyelectrolyte weight ratio greaterthan 1.2 (specifically, 2.5), exhibit no measurable increases in DryPrecipitate Mass Yield compared to their corresponding ComparativeExamples containing no anionic polyelectrolyte, C15, C17, C19 and C21,respectively.

TABLE 4a wt % active material Material Material class C15 E11 C16Acylates Copolymer Anionic polyelectrolyte 0 0.1 1.5 Guar Cationicpolyelectrolyte 0.6 0.6 0.6 Hydroxypropyltrimonium Chloride SodiumLaureth Sulfate Anionic surfactant 3.5 3.5 3.5 Cocamidopropyl BetaineAmphoteric 3.5 3.5 3.5 zwitterionic surfactant Sodium Chloride Salt 0.40.4 0.4 Sodium Benzoate Preservative 0.5 0.5 0.5 Citric Acid pH adjusterq.s. q.s. q.s. Sodium Hydroxide pH adjuster q.s. q.s. q.s. Water Vehicleq.s. to 100 wt % q.s. to 100 wt % q.s. to 100 wt % Anionicpolyelectrolyte/cationic polyelectrolyte 0.00 0.17 2.50 active weightratio Dry Precipitate Mass Yield 2.19 2.7 0

TABLE 4b wt % active material Material Material class C17 E12 C18Acylates Copolymer Anionic polyelectrolyte 0 0.1 1.5 Polyquaternium-5Cationic polyelectrolyte 0.6 0.6 0.6 Sodium Laureth Sulfate Anionicsurfactant 3.5 3.5 3.5 Cocamidopropyl Betaine Amphoteric/ 3.5 3.5 3.5zwitterionic surfactant Sodium Chloride Salt 0.4 0.4 0.4 Sodium BenzoatePreservative 0.5 0.5 0.5 Citric Acid pH adjuster q.s. q.s. q.s. SodiumHydroxide pH adjuster q.s. q.s. q.s. Water Vehicle q.s. to 100 wt % q.s.to 100 wt % q.s. to 100 wt % Anionic polyelectrolyte/cationicpolyelectrolyte 0.00 0.17 2.50 active weight ratio Dry Precipitate MassYield 0 0.46 0

TABLE 4c wt % active material Material Material class C19 E13 C20Acylates Copolymer Anionic polyelectrolyte 0 0.1 1.5 Polyquaternium-28Cationic polyelectrolyte 0.6 0.6 0.6 Sodium Laureth Sulfate Anionicsurfactant 3.5 3.5 3.5 Cocamidopropyl Betaine Amphoteric/ 3.5 3.5 3.5zwitterionic surfactant Sodium Chloride Salt 0.4 0.4 0.4 Sodium BenzoatePreservative 0.5 0.5 0.5 Citric Acid pH adjuster q.s. q.s. q.s. SodiumHydroxide pH adjuster q.s. q.s. q.s. Water Vehicle q.s. to 100 wt % q.s.to 100 wt % q.s. to 100 wt % Anionic polyelectrolyte/cationicpolyelectrolyte 0.00 0.17 2.50 active weight ratio Dry Precipitate MassYield 0 0.9 0

TABLE 4d wt % active material Material Material class C21 E14 C22Acylates Copolymer Anionic polyelectrolyte 0 0.1 1.5 Polyquaternium-44Cationic polyelectrolyte 0.6 0.6 0.6 Sodium Laureth Sulfate anionicsurfactant 3.5 3.5 3.5 Cocamidopropyl Betaine Amphoteric/ 3.5 3.5 3.5zwitterionic surfactant Sodium Chloride Salt 0.4 0.4 0.4 Sodium BenzoatePreservative 0.5 0.5 0.5 Citric Acid pH adjuster q.s. q.s. q.s. SodiumHydroxide pH adjuster q.s. q.s. q.s. Water Vehicle q.s. to 100 wt % q.s.to 100 wt % q.s. to 100 wt % Anionic polyelectrolyte/cationicpolyelectrolyte 0.00 0.17 2.50 active weight ratio Dry Precipitate MassYield 0.99 2.33 0.7

Example 5 Precipitation Measurements of Inventive (E15-E17) andComparative (C7, C11, C23, C24) Examples Using a Non-Crosslinked, LowMolecular Weight Anionic Polyelectrolyte

Comparative Examples C7, C11, C23 and C24 and Inventive ExamplesE15-E17, listed in Table 5a, along with Dry Precipitate Mass Yield (asmeasured in accord with the Dry Precipitate Mass Yield Test as describedherein), are formulations similar to compositions from Tables 2a and 3b,incorporating PQ-7 in with different ratios of SLES and CAPB; however,in this case, the compositions incorporate an alternate anionicpolyelectrolyte, specifically, Potassium Acrylates Copolymer. Unlike theAcrylates Copolymer (Carbopol® AQUA SF-1), which is crosslinked,Potassium Acrylates Copolymer is a non-crosslinked polyelectrolyte witha comparatively low molecular weight. As shown in Tables 5a and 5b,Inventive Examples E15-E17 exhibit measurable increases in DryPrecipitate Mass Yield compared to corresponding Comparative Examplescontaining no anionic polyelectrolyte, C11 and C7. Comparative ExamplesC23 and C24, which have an anionic to cationic polyelectrolyte weightratio greater than 1.2 (specifically, 2.5), exhibits no measurableincrease in Dry Precipitate Mass Yield compared to its correspondingComparative Examples containing no anionic polyelectrolyte, C11 and C7,respectively.

TABLE 5a wt % active material Material Material class C11 E15 E16 C23Potassium Acrylates Anionic 0 0.1 0.5 1.5 Copolymer polyelectrolytePolyquaternium-7 Cationic 0.6 0.6 0.6 0.6 polyelectrolyte Sodium LaurethSulfate Anionic 3.5 3.5 3.5 3.5 surfactant Cocamidopropyl BetaineAmphoteric/ 3.5 3.5 3.5 3.5 zwitterionic surfactant Sodium Chloride Salt0.4 0.4 0.4 0.4 Sodium Benzoate Preservative 0.5 0.5 0.5 0.5 Citric AcidpH adjuster q.s. q.s. q.s. q.s. Sodium Hydroxide pH adjuster q.s. q.s.q.s. q.s. Water Vehicle q.s. to 100 wt % q.s. to 100 wt % q.s. to 100 wt% q.s. to 100 wt % Anionic polyelectrolyte/cationic 0.00 0.17 0.83 2.50polyelectrolyte active weight ratio Dry Precipitate Mass Yield 0.37 0.630.67 0

TABLE 5b wt % active material Material Material class C7 E17 C24Potassium Acrylates Copolymer Anionic 0 0.1 1.5 polyelectrolytePolyquaternium-7 Cationic 0.6 0.6 0.6 polyelectrolyte Sodium LaurethSulfate Anionic surfactant 9 9 9 Cocamidopropyl Betaine Amphoteric/ 2 22 zwitterionic surfactant Sodium Chloride Salt 0.4 0.4 0.4 SodiumBenzoate Preservative 0.5 0.5 0.5 Citric Acid pH adjuster q.s. q.s. q.s.Sodium Hydroxide pH adjuster q.s. q.s. q.s. Water Vehicle q.s. to 100 wt% q.s. to 100 wt % q.s. to 100 wt % Anionic polyelectrolyte/cationicpolyelectrolyte 0.00 0.17 2.50 active weight ratio Dry Precipitate MassYield 0 0.21 0

Example 6 Preparation and Precipitation Measurements of ComparativeExamples (C25-C28)

Comparative Examples C25 & C26, described in Table 6a, are made toreplicate Examples 10 and 11 of International Patent Application WO2005/023969. The selection of raw materials and formulation processesreplicates the materials and process referenced in this publication,given available commercial materials. These compositions were made asfollows:

50 wt % of DI water was added to a beaker. If included, AcrylatesCopolymer was added to the water with mixing. The PEG-80 SorbitanLaurate was then added thereto with mixing. The following ingredientswere added thereto independently with mixing until each respectiveresulting mixture was homogeneous: Cocamidopropylbetaine (Tego BetainL7V), Sodium Trideceth Sulfate, Glycerin, Polyquaternium-10,Quaternium-15 and Tetrasodium EDTA. The pH of the resulting solution wasthen adjusted with either a 20 wt % Sodium Hydroxide solution or a 20 wt% Citric Acid solution until a final pH of about 6.3-6.6 was obtained.The remainder of the water was then added thereto.

Dry Precipitate Mass Yield was measured in accord with the DryPrecipitate Mass Yield Test as described herein. As listed in Table 6a,Comparative Example C26 has an anionic to cationic polyelectrolyteweight ratio of 1.86 and exhibits no measurable increase in DryPrecipitate Mass Yield compared to their corresponding ComparativeExamples containing no anionic polyelectrolyte, C25.

TABLE 6a wt % active material Material C25 C26 Acrylates Copolymer 0.000.26 Polyquaternium-10 0.14 0.14 Sodium Trideceth Sulfate 6.00 6.00Cocamidopropyl Betaine 3.40 3.40 PEG-80 Sorbitan Laurate 3.30 3.30Glycerin 1.88 1.88 Tetrasodium EDTA 0.26 0.26 Quaternium-15 0.05 0.05Sodium Hydroxide q.s. q.s. Citric Acid q.s. q.s. Water q.s. to 100 wt %q.s. to 100 wt % Anionic polyelectrolyte/cationic 0.00 1.86polyelectrolyte active weight ratio Dry Precipitate Mass Yield 0   0  

Comparative Examples C27 & C28, described in Table 6b, were made tomodel Examples 4 and 1 in U.S. Pat. No. 7,776,318, respectively. Theonly modification to these formulations is the exclusion of glycoldistearate, an opacifier which is not solubilized in formulations andsediments out upon dilution. Such suspended solids interfere with theDry Precipitate Mass Yield Test described herein, and are thus excludedfrom the following formulation to provide unobstructed insight into thepolyelectrolyte precipitation properties of these compositions. Theselection of raw materials and formulation processes otherwisereplicates the materials and process referenced in this patent, givencurrently available commercial materials. These compositions were madeas follows:

Water, preserving agents, glycerin and hexylene glycol were added to anappropriately sized vessel equipped with a hotplate and overheadmechanical stirrer. Once the batch was heated to 50° C., some of thesodium laureth sulfate was added until fully dissolved. Then,sequentially, Disodium EDTA, Polyquaternium-7, and Acrylates Copolymerwere added, with sufficient time given between each additionalingredient to observe complete and even dispersal. The pH of thesolution was then adjusted to 6.4-6.6 through addition of dilute sodiumhydroxide. Fragrance was then added to the mixture.

Subsequently, Coco-Betaine, then Disodium Cocoamphodiacetate are added.Sodium Glycolate and Sodium Chloride are added after that. Finally, thepH of the solution was adjusted using dilutions of sodium hydroxideand/or citric acid to a pH of 6.4-6.6 (for Examples containing PhenonipXB as a preservative) and the remaining water was added in q.s. to 100wt %. The batch was allowed to mix until uniform before being dischargedto an appropriate storage vessel.

Dry Precipitate Mass Yield was measured in accord with the DryPrecipitate Mass Yield Test as described herein. As listed in Table 6b,the composition C28 has an anionic to cationic polyelectrolyte weightratio of 2.36 and exhibits no measurable increase in Dry PrecipitateMass Yield compared to the corresponding Comparative Examples containingno anionic polyelectrolyte, C27.

TABLE 6b wt % active material Material C27 C28 Acrylates Copolymer 00.26 Polyquaternium-7 0.11 0.11 Sodium Laureth Sulfate 9.8 9.8Coco-Betaine 1.99 1.99 Disodium Cocoamphodiacetate 0.6 0.6 Glycerin 1 1Hexylene Glycol 1 1 Disodium EDTA 0.26 0.26 Sodium Glycolate 0.12 0.12Sodium Chloride 2.16 2.16 Fragrance 0.25 0.25 Preservative (Phenonip XB)1 1 Sodium Hydroxide q.s. q.s. Citric Acid q.s. q.s. Water q.s. to 100wt % q.s. to 100 wt % Anionic polyelectrolyte/cationic 0.00 2.36polyelectrolyte active weight ratio Dry Precipitate Mass Yield 0 0

Examples 7a Through 7g Precipitation Measurements of Inventive (E18-E24)and Comparative Examples (C9, C11, C29-32) Using a Variety of AnionicPolyelectrolyte Chemistries

Comparative Examples C9, C11, C29-34 and Inventive Examples E18-E24,listed in Tables 7a-7g, along with Dry Precipitate Mass Yield (asmeasured in accord with the Dry Precipitate Mass Yield Test as describedherein), are formulations which replicate select anionicpolyelectrolyte, salt and preservative levels from Table 3a-3b, but usedifferent concentrations and chemistries of anionic polyelectrolyte. Asshown in Tables 7a Through 7g, Inventive Examples E18-E24 exhibit ameasurable increases in Dry Precipitate Mass Yield compared to theircorresponding Comparative Examples containing no anionicpolyelectrolyte, C9 and C11. Comparative Examples C29-34, which have ananionic to cationic polyelectrolyte weight ratio greater than 1.2(specifically, 2.5 or 3.33), exhibit no measurable increases in DryPrecipitate Mass Yield compared to their corresponding ComparativeExamples containing no anionic polyelectrolyte, C9 and C11.

TABLE 7a wt % active material Material Material class C9 E18 C29Polyacrylate-33 Anionic 0 0.1 2 polyelectrolyte Polyquaternium-10Cationic 0.6 0.6 0.6 polyelectrolyte Sodium Laureth Anionic 3.5 3.5 3.5Sulfate surfactant Cocamidopropyl Amphoteric/ 3.5 3.5 3.5 Betainezwitterionic surfactant Sodium Chloride Salt 0.4 0.4 0.4 Sodium BenzoatePreservative 0.5 0.5 0.5 Citric Acid pH adjuster q.s. q.s. q.s. SodiumHydroxide pH adjuster q.s. q.s. q.s. Water Vehicle q.s. to q.s. to q.s.to 100 wt % 100 wt % 100 wt % Anionic polyelectrolyte/cationic 0.00 0.173.33 polyelectrolyte active weight ratio Dry Precipitate Mass Yield 2.73.3 0

TABLE 7b wt % active material Material Material class C9 E19 C30Carboxymethycellulose Anionic 0 0.1 1.5 polyelectrolytePolyquaternium-10 Cationic 0.6 0.6 0.6 polyelectrolyte Sodium LaurethSulfate Anionic 3.5 3.5 3.5 surfactant Cocamidopropyl Amphoteric/ 3.53.5 3.5 Betaine zwitterionic surfactant Sodium Chloride Salt 0.4 0.4 0.4Sodium Benzoate Preservative 0.5 0.5 0.5 Citric Acid pH adjuster q.s.q.s. q.s. Sodium Hydroxide pH adjuster q.s. q.s. q.s. Water Vehicle q.s.to q.s. to q.s. to 100 100 100 wt % wt % wt % Anionicpolyelectrolyte/cationic 0.00 0.17 2.50 polyelectrolyte active weightratio Dry Precipitate Mass Yield 2.7 3.32 1.11

TABLE 7c wt % active material Material Material class C11 E20 C31Xanthan Gum Anionic 0 0.1 1.5 polyelectrolyte Polyquaternium-10 Cationic0.6 0.6 0.6 polyelectrolyte Sodium Laureth Anionic 3.5 3.5 3.5 Sulfatesurfactant Cocamidopropyl Amphoteric/ 3.5 3.5 3.5 Betaine zwitterionicsurfactant Sodium Chloride Salt 0.4 0.4 0.4 Sodium Benzoate Preservative0.5 0.5 0.5 Citric Acid pH adjuster q.s. q.s. q.s. Sodium Hydroxide pHadjuster q.s. q.s. q.s. Water Vehicle q.s. to q.s. to q.s. to 100 wt %100 wt % 100 wt % Anionic polyelectrolyte/cationic 0.00 0.17 2.50polyelectrolyte active weight ratio Dry Precipitate Mass Yield 2.7 3.131.23

TABLE 7d wt % active material Material Material class C11 E21 C32Polyacrylate-33 Anionic 0 0.1 2 polyelectrolyte Polyquaternium-7Cationic 0.6 0.6 0.6 polyelectrolyte Sodium Laureth Anionic 3.5 3.5 3.5Sulfate surfactant Cocamidopropyl Amphoteric/ 3.5 3.5 3.5 Betainezwitterionic surfactant Sodium Chloride Salt 0.4 0.4 0.4 Sodium BenzoatePreservative 0.5 0.5 0.5 Citric Acid pH adjuster q.s. q.s. q.s. SodiumHydroxide pH adjuster q.s. q.s. q.s. Water Vehicle q.s. to q.s. to q.s.to 100 wt % 100 wt % 100 wt % Anionic polyelectrolyte/cationic 0.00 0.173.33 polyelectrolyte active weight ratio Dry Precipitate Mass Yield 0.371.65 0

TABLE 7e wt % active material Material Material class C11 E22 C33Carboxymethycellulose Anionic 0 0.1 1.5 polyelectrolyte Polyquaternium-7Cationic 0.6 0.6 0.6 polyelectrolyte Sodium Laureth Anionic 3.5 3.5 3.5Sulfate surfactant Cocamidopropyl Amphoteric/ 3.5 3.5 3.5 Betainezwitterionic surfactant Sodium Chloride Salt 0.4 0.4 0.4 Sodium BenzoatePreservative 0.5 0.5 0.5 Citric Acid pH adjuster q.s. q.s. q.s. SodiumHydroxide pH adjuster q.s. q.s. q.s. Water Vehicle q.s. to q.s. to q.s.to 100 100 100 wt % wt % wt % Anionic polyelectrolyte/cationic 0.00 0.172.50 polyelectrolyte active weight ratio Dry Precipitate Mass Yield 0.370.55 0.23

TABLE 7f wt % active material Material Material class C11 E23 C34Xanthan Gum Anionic 0 0.1 1.5 polyelectrolyte Polyquaternium-7 Cationic0.6 0.6 0.6 polyelectrolyte Sodium Laureth Anionic 3.5 3.5 3.5 Sulfatesurfactant Cocamidopropyl Amphoteric/ 3.5 3.5 3.5 Betaine zwitterionicsurfactant Sodium Chloride Salt 0.4 0.4 0.4 Sodium Benzoate Preservative0.5 0.5 0.5 Citric Acid pH adjuster q.s. q.s. q.s. Sodium Hydroxide pHadjuster q.s. q.s. q.s. Water Vehicle q.s. to q.s. to q.s. to 100 wt %100 wt % 100 wt % Anionic polyelectrolyte/cationic 0.00 0.17 2.50polyelectrolyte active weight ratio Dry Precipitate Mass Yield 0.37 0.520.10

TABLE 7g wt % active material Material Material class C11 E24 SodiumPolyacrylate Anionic 0 0.1 (crosslinked) polyelectrolytePolyquaternium-7 Cationic 0.6 0.6 polyelectrolyte Sodium Laureth SulfateAnionic surfactant 3.5 3.5 Cocamidopropyl Betaine Amphoteric/ 3.5 3.5zwitterionic surfactant Sodium Chloride Salt 0.4 0.4 Sodium BenzoatePreservative 0.5 0.5 Citric Acid pH adjuster q.s. q.s. Sodium HydroxidepH adjuster q.s. q.s. Water Vehicle q.s. to q.s. to 100 wt % 100 wt %Anionic polyelectrolyte/cationic polyelectrolyte 0.00 0.17 active weightratio Dry Precipitate Mass Yield 0.37 0.56

Examples 8a Through 8e Comparisons of Rheological Properties ofInventive (E1-E3, E7-E9, E18-E20) and Comparative Examples (C1-C3,C7-C12, C29-31)

A selection of the previously listed Comparative and Inventive Exampleswere tested according to the Viscosity Tests and Yield Stress Testsdescribed herein. The rheological properties of compositions describedin Table 1a are listed in Table 8a. The amount of Acrylates Copolymerincluded in Inventive Examples E1-E3, which demonstrate enhancedprecipitation (as previously shown in Table 1a), is not sufficient toincrease measured viscosity above η_(min), the minimum value needed todenote a significant/perceptible change in viscosity compared to thesystem with no anionic polyelectrolyte described herein. Likewise, theinventive compositions E1-E3 exhibit no measurable yield stress value.Only in Comparative Examples C2-C3 (which do not exhibit enhancedprecipitation) is there sufficient Acrylates Copolymer (1-1.5 wt %) tocause a measurable yield stress and significant increase in viscosity.Therefore, the use of the crosslinked ASE Acrylates Copolymer inInventive Examples E1-E3 falls outside of the polyelectrolyte'sprescribed use as a suspending agent, thickener, or rheology modifier.

TABLE 8a Rheological properties for composition containing 9 wt % SLES,2 wt % CAPB and 0.6 wt % PQ-10 Anionic Anionic polyelectrolytepolyelectrolyte/cationic Yield concentration polyelectrolyte stressExample (active wt %) active weight ratio (Pa) η_(min) (cps) C1 0 0.000.00 569.02 Rheological properties for compositions containing 9 wt %SLES, 2 wt % CAPB, 0.6 wt % PQ-10 and Acrylates Copolymer AcrylatesAnionic Copolymer polyelectrolyte/cationic Yield Mid-shear concentrationpolyelectrolyte stress viscosity Example (active wt %) active weightratio (Pa) η (cps) E1 0.1 0.17 0.00 96.1 E2 0.3 0.50 0.00 175.1 E3 0.61.00 0.00 465.5 C2 1 1.67 1.97 1515 C3 1.5 2.50 8.66 4435The use of Acrylates Copolymer is similarly shown to not impartmeasurable yield stress or significant changes in viscosity in InventiveExamples including varying surfactant blends and cationicpolyelectrolyte chemistries, and shown in Tables 8b-8d.

TABLE 8b Rheological properties for composition containing 9 wt % SLES,2 wt % CAPB and 0.6 wt % PQ-7 Anionic Anionic polyelectrolytepolyelectrolyte/cationic Yield concentration polyelectrolyte stressExample (active wt %) active weight ratio (Pa) η_(min) (cps) C7 0 0.000.00 286.68 Rheological properties for compositions containing 9% SLES,2% CAPB, 0.6% PQ-7 and Acrylates Copolymer Acrylates Anionic Copolymerpolyelectrolyte/cationic Yield Mid-shear concentration polyelectrolytestress viscosity Example (active wt %) active weight ratio (Pa) η (cps)E7 0.1 0.17 0.00 24.06 C8 1.5 2.50 7.05 3426

TABLE 8c Rheological properties for composition containing 3.5 wt %SLES, 3.5 wt % CAPB and 0.6 wt % PQ-10 Anionic Anionic polyelectrolytepolyelectrolyte/cationic Yield concentration polyelectrolyte stressExample (active wt %) active weight ratio (Pa) η_(min) (cps) C11 0 0.000.00 3126 Rheological properties for compositions containing 9 wt %SLES, 2 wt % CAPB, 0.6 wt % PQ-10 and Acrylates Copolymer AcrylatesAnionic Copolymer polyelectrolyte/cationic Yield Mid-shear concentrationpolyelectrolyte stress viscosity Example (active wt %) active weightratio (Pa) η (cps) E9 0.1 0.17 0.00 1626 C12 1.5 2.50 8.65 4963

TABLE 8d Rheological properties for composition containing 3.5 wt %SLES, 3.5 wt % CAPB and 0.6 wt % PQ-7 Anionic Anionic polyelectrolytepolyelectrolyte/cationic Yield concentration polyelectrolyte stressExample (active wt %) active weight ratio (Pa) η_(min) (cps) C9 0 0.000.00 1406 Rheological properties for compositions containing 3.5 wt %SLES, 3.5 wt % CAPB, 0.6 wt % PQ-7 and Acrylates Copolymer AcrylatesAnionic Copolymer polyelectrolyte/cationic Yield Mid-shear concentrationpolyelectrolyte stress viscosity Example (active wt %) active weightratio (Pa) η (cps) E8 0.1 0.17 0.00 1347 C10 1.5 2.50 12.52 4435The rheological properties of Inventive Examples E18 and E19, which usealternative anionic rheology modifying polyelectrolytes (specifically,Carboxymethylcellose, Polyacrylate-33 and Xanthan Gum) are displayed inTable 8e. Again, the use of these anionic polyelectrolytes at the lowlevels necessary for increased polyelectrolyte precipitation does notimpart a yield stress or significant changes in viscosity. Therefore,the use of these alternate anionic rheology modifiers in InventiveExamples falls outside of their prescribed use as suspending agents,thickeners, or viscosity modifiers.

TABLE 8e Viscosity for formulation containing 3.5 wt % SLES, 3.5 wt %CAPB and 0.6 wt % PQ-10 Anionic Anionic polyelectrolytepolyelectrolyte/cationic Yield concentration polyelectrolyte stressExample (active wt %) active weight ratio (Pa) η_(min) (cps) C11 0 0.000.00 3782 Rheological properties for compositions containing 3.5 wt %SLES, 3.5 wt % CAPB and 0.6 wt % PQ-10 and Acrylates Copolymer AcrylatesAnionic Copolymer polyelectrolyte/cationic Yield Low-shear concentrationpolyelectrolyte stress viscosity Example (active wt %) active weightratio (Pa) η (cps) E9 0.1 0.17 0.00 2065 C12 1.5 2.50 8.66 12520Rheological properties for compositions containing 3.5 wt % SLES, 3.5 wt% CAPB and 0.6 wt % PQ-10 and Carboxymethylcellulose Carboxy- Anionicmethylcellulose polyelectrolyte/cationic Yield Low-shear concentrationpolyelectrolyte stress viscosity Example (active wt %) active weightratio (Pa) η (cps) E19 0.1 0.17 0.00 3470 C30 1.5 2.50 0.00 20970Rheological properties for compositions containing 3.5 wt % SLES, 3.5 wt% CAPB and 0.6 wt % PQ-10 and Polyacrylate-33 Anionic Polyacrylate-33polyelectrolyte/cationic Yield Low-shear concentration polyelectrolytestress viscosity Example (active wt %) active weight ratio (Pa) η (cps)E18 0.1 0.17 0.00 2553 C29 1.5 2.50 4.94 6321 Rheological properties forcompositions containing 3.5 wt % SLES, 3.5 wt % CAPB and 0.6 wt % PQ-10and Xanthan Gum Anionic Xanthan Gum polyelectrolyte/cationic YieldLow-shear concentration polyelectrolyte stress viscosity Example (activewt %) active weight ratio (Pa) η (cps) E20 0.1 0.17 0.00 2743 C31 1.52.50 0.00 27190

Example 9 Comparison of Cleanser Polyelectrolyte Film Deposition on anIn-Vitro Substrate Between Inventive (E1) and Comparative Examples (C1,C3)

The film/polyelectrolyte deposition efficacy of a set of Comparative andInventive Examples with comparable compositions except for concentrationof anionic polyelectrolyte (C1, E1 and C3, described in Table 1a) isevaluated according to the Ellipsometry-based Polyelectrolyte DepositionTest as described herein. The results seen in Table 9 show thatInventive Examples E1 demonstrates an increase of deposited filmthickness of ˜40% compared to the Comparative Examples C1 and C3 (withanionic/cationic polyelectrolyte active weight ratios 0 and 2.5,respectively).

TABLE 9 Anionic/ Average Acrylates cationic deposited PQ-10 Copolymerpolyelectrolyte film concentration concentration active weight thicknessExample (wt % active) (wt % active) ratio (nm) C1 0.6 0 0 1.10 E1 0.60.1 0.17 1.63 C3 0.6 1.5 2.5 1.25

Example 10 Evaluation and Comparison of Skin Feel Between InventiveExample (E9) and Comparative Example (C11)

Skin feel after washing with Comparative Example C8 and InventiveExample E6 (with comparable compositions except for concentration ofanionic polyelectrolyte, described in Table 3b) and then drying werecompared qualitatively by three volunteers according to a SensoryEvaluation Test. In this test, for the purpose of skin equilibration,participants first wash their hands and forearms with 1 mL of a standardsurfactant solution (5 wt % active Sodium Laureth Sulfate, 5 wt % activeCocamidopropyl Betaine, pH 4.5, DI water). After thorough rinsing (60sec at ˜3 liters per minute with 35-45° C. tap water), 1 mL of a testcomposition (C8 or E6, respectively) was dispensed into the wet palm.Participants wash their wet hands and forearms for 30 sec by applyingcircular motions of the hands on the forearms. After rinsing (30 sec at˜3 liters per minute with 35-45° C. tap water), participants dabbedtheir hands and forearms dry with a paper towel, and let their hands andarms air-dry completely for approximately 120 sec. They then describethe sensory feel of their skin by letting fingers glide over their handsand forearms. Descriptions of the dry feel of skin after use of theComparative and Inventive Examples are listed in Table 10. It is shownhere that the addition of 0.1 wt % of Acrylates Copolymer not onlysignificantly increases the amount of precipitate measured in theRelative Dry Precipitate Mass Yield Test (as displayed in Table 1a), butalso changes the general consensus on resulting skin feel from cleansingfrom “soft” to “powdery” after drying. This indicates a change in thetactile properties of the deposited film.

TABLE 10 Example C11 Example E9 PQ-7 concentration (active wt %) 0.6 0.6Acrylates Copolymer (active wt %) 0 0.1 Anionic polyelectrolyte/cationic0 0.17 polyelectrolyte active weight ratio Comments from subjects “soft,slippery, not “smooth, powdery” powdery”, satin-like”

Example 11 Comparison of Dimethicone Deposition from Formulation Use onHuman Skin Between Inventive (E11) and Comparative (C15) Examples

The dimethicone deposition efficacy of a pair of Comparative andInventive Examples containing 0.6 wt % Guar HydroxypropyltrimoniumChloride, with identical compositions except for concentration ofanionic polyelectrolyte, C15 (no anionic polyelectrolyte) and E11 (0.1wt % Acrylates Copolymer) (as described in Table 4a above) wereevaluated according to the Dimethicone Deposition Test as describedherein. The Si peak intensity at 1260 cm⁻¹, which correlates to theconcentration of dimethicone on human skin, is shown in Table 11. Thesedata indicate a marked improvement in dimethicone deposition from theComparative Example C15 to the Inventive Example E11.

TABLE 11 Anionic/cationic polyelectrolyte Si peak intensity activeweight @ 1260 cm−1 Example ratio (a.u.) C15 0 55 E11 0.17 234

1-15. (canceled)
 16. A composition, comprising, in a cosmeticallyacceptable aqueous medium, a) a cationic polyelectrolyte, b) at leastone surfactant; and (c) from about 0.01 to about 1.2 weight percent ofan anionic polyelectrolyte, wherein the anionic polyelectrolyte is oneof an alkali-swellable emulsion polymer or a hydrophobically modifiedalkali swellable emulsion polymer, wherein the weight ratio of saidanionic polyelectrolyte to said cationic polyelectrolyte is from about0.05 to about 1.2, wherein said composition exhibits a viscosity changethat is below a minimum significant-change-threshold (Δη_(min)) andexhibits no measurable yield stress or increase in yield stress valuewhen compared to a substantially identical composition that does notcontain from about 0.01 to about 1.2 weight percent of said anionicpolyelectrolyte, at a weight ratio of anionic polyelectrolyte tocationic polyelectrolyte of from about 0.05 to about 1.2.
 17. Thecomposition of claim 16 wherein the weight ratio of said anionicpolyelectrolyte to said cationic polyelectrolyte is about 0.1 toabout
 1. 18. The composition of claim 16 comprising from about 0.1weight percent to about 1 weight percent of said anionicpolyelectrolyte.
 19. The composition of claim 16 comprising from about0.1 weight percent to about 1 weight percent of said cationicpolyelectrolyte.
 20. The composition of claim 16 comprising from about0.1 weight percent to about 0.8 weight percent of said cationicpolyelectrolyte.
 21. The composition of claim 16 comprising from about0.2 weight percent to about 0.6 weight percent of said cationicpolyelectrolyte.
 22. The composition of claim 16 comprising from about 1weight percent to about 25 weight percent of said surfactant.
 23. Thecomposition of claim 16 comprising from about 3 weight percent to about15 weight percent of said surfactant.
 24. The composition of claim 16wherein a Dry Precipitate Mass Yield upon dilution of said compositionis greater than of a Dry Precipitate Mass Yield upon dilution of asubstantially identical composition that does not comprise from about0.01 weight percent to about 1.2 weight percent of said anionicpolyelectrolyte, at a weight ratio of said anionic polyelectrolyte tosaid cationic polyelectrolyte of from about 0.05 to about
 1. 25. Thecomposition of claim 16 wherein a Dry Precipitate Mass Yield upondilution of said composition is increased by 10% or more compared to asubstantially identical composition that does not contain from about0.01 to about 1.2 weight percent of said anionic polyelectrolyte, at aweight ratio of anionic polyelectrolyte to cationic polyelectrolyte offrom about 0.05 to about 1.2.
 26. The composition of claim 16 wherein aDry Precipitate Mass Yield upon dilution of said composition isincreased by 20% or more compared to a substantially identicalcomposition that does not comprise from about 0.01 weight percent toabout 1.2 weight percent of said anionic polyelectrolyte.
 27. Thecomposition of claim 16 wherein a Dry Precipitate Mass Yield upondilution of said composition is increased by 40% or more compared to asubstantially identical composition that does not comprise from about0.01 weight percent to about 1.2 weight percent of said anionicpolyelectrolyte.
 28. The composition of claim 16 wherein said anionicpolyelectrolyte is selected from the group consisting ofpolyelectrolytes derived from ethylenically unsaturated monomerscontaining anionic and anionically-ionizable monomers, anionic andanionically ionizable polysaccharides and polysaccharide derivativesthereof and anionic or anionically ionizable polypeptides or proteins orhybrid (co)polymers.
 29. The composition of claim 16 wherein saidcationic polyelectrolyte is selected from the group consisting ofpolyelectrolytes derived from ethylenically unsaturated monomerscontaining cationic protonated amine or quaternary ammoniumfunctionalities, cationic and cationically-ionizable polysaccharides andpolysaccharide derivatives thereof, and cationic orcationically-ionizable polypeptides or proteins or hybrid (co)polymers.30. The composition of claim 16 wherein said surfactant is selected fromthe group consisting of anionic, zwitterionic, nonionic and cationicsurfactants.